WO2019069889A1 - Parasitic plant germination regulator - Google Patents

Abstract

Provided are a compound having parasitic plant germination regulatory activity (especially parasitic plant germination induction activity), and a parasitic plant germination regulator in which said compound is used. A compound represented by general formula (1) [in the formula, R1 represents a group derived from a heterocycle containing a nitrogen atom; R2 represents a divalent group that is a linker; R3 represents an optionally substituted aryl group, an optionally substituted heteroaryl group, an optionally substituted cycloalkyl group, or a C1-6 alkyl group; and R4, R5, and R6 are the same or different and represent a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted alkynyl group].

Description

Parasitic plant germination regulator

The present invention relates to a compound useful as a parasitic plant germination regulator, and to a parasitic plant germination regulator.

Parasitic plants typified by plants belonging to the genus Striga (sometimes abbreviated as "striga" in this specification) are parasitic on main crops such as corn, rice, legumes and the like to cause poor growth. The damage has spread to Africa, Asia, Australia, the United States, etc., and the amount of damage is estimated to reach US $ 10 billion annually in Africa.

Seeds of parasitic plants can survive in soil for a long period of time, sense sprouting stimulants (such as strigolactones) secreted from the roots of surrounding host crops, and thus germinate, as a host crop. Parasitic on the roots of And, the seeds produced by the plants of the parasitic plants that appear on the ground contaminate the surrounding soil. For this reason, once the soil is contaminated with seeds of parasitic plants, if no measures are taken, parasitic plant damage will continue in the soil, and the soil area contaminated with seeds will gradually expand. It will be.

As a countermeasure against parasitic plants, it is said that applying a parasitic plant germination regulator to soil contaminated with seeds of parasitic plants is effective. For example, if a parasitic plant germination-inducing agent is applied in an environment where there is no host plant, the germinating parasitic plant will not be able to parasitize and will die, which makes it possible to clean the soil. Therefore, there is a need for the development of substances that more efficiently induce germination of parasitic plants.

Strigolactone and its derivatives are disclosed, for example, in Non-Patent Document 1. Strigolactone is a carotenoid derivative,

As represented by the above, it is characterized by a complex basic skeleton in which one more lactone ring (D ring) is linked via an enol ether to a tricyclic terpenoid (ABC ring) containing a lactone ring, It has many asymmetric centers. In addition, strigolactone and its derivatives are known to be present in root exudates of many plants, and have plant hormone action such as suppressing the growth of branches (Non-patent Document 2).

For example, Patent Document 1 discloses a compound having a basic skeleton different from strigolactone and its derivative. The carbamate compound shown in Patent Document 1 can be obtained by inducing 3-methylbutenolide to carbamate, but the expression of germination stimulating activity shown in Patent Document 1 requires a high concentration of 10 μM, and it is a strigolac It is assumed to be less active than ton and its derivatives.

WO 2011/125714 International Publication No. 2017/002898

The present inventor has reported that a compound having a basic skeleton different from that of strigolactone and its derivative has a stripe sprouting control activity (Patent Document 2), but in the course of earnest research, it is a sprouting-inducing activity, synthesis We considered that there is room for further improvement from the viewpoint of costs etc.

An object of the present invention is to provide a compound having parasitic plant germination regulatory activity (in particular, parasitic plant germination inducing activity), and a parasitic plant germination regulator using the compound.

MEANS TO SOLVE THE PROBLEM As a result of advancing earnest research in view of a subject, the present inventors discovered that the compound represented by General formula (1) has parasitic plant sprout control activity (especially parasitic plant sprout induction activity).

That is, the present invention includes the following aspects.

Item 1. General formula (1):

[Wherein, R ¹ represents a group derived from a hetero ring containing a nitrogen atom. R ² represents a divalent group which is a linker. R ³ represents an aryl group which may be substituted, a heteroaryl group which may be substituted, a cycloalkyl group which may be substituted, or an alkyl group having 1 to 6 carbon atoms. R ⁴ , R ⁵ and R ⁶ are the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group which may be substituted, an alkenyl group which may be substituted, or an alkynyl group which may be substituted. However, when the hetero ring is a polycycle, two bonds of R ¹ are present in ^one of a plurality of rings constituting the polycycle. ]
A compound represented by

Item 2. The R ¹ is a general formula (Y):

[Wherein, R ¹¹ represents-(CHR ^11a- ) _n (n represents an integer of 1 to 3. R ^11a is the same or different and represents a hydrogen atom or an alkyl group, and when n is 2 or 3, two of them R ^11a may be bonded to each other to form a ring with the adjacent carbon atom. R ¹² and R ¹³ are the same or different and each represents a hydrogen atom or an alkyl group, and R ¹² and R ¹³ may be bonded to each other to form a ring with adjacent carbon atoms. R ¹⁴ represents a carbon or nitrogen atom. ]
Or a divalent group represented by the general formula (Y ′):

[Wherein, R ¹⁵ represents a single bond or-(CHR ^15a- ) _m (m represents 1 or 2. R ^15a is the same or different and represents a hydrogen atom or an alkyl group, and when m is 2, adjacent 2 One R ^15a may be bonded to each other to form a ring with the adjacent carbon atom. R ¹⁶ and R ¹⁷ are the same or different and each represents a hydrogen atom or an alkyl group, and R ¹⁶ and R ¹⁷ may be bonded to each other to form a ring with adjacent carbon atoms. ]
Item 2. The compound according to item 1, which is a divalent group represented by

Item 3. Wherein R ² is Formula (Z1): - T-U- ( wherein (Z1), T is, -S (O) _1-2 -, or -C (= O) -, or - (CH _{2) 1-3} - and, U is a single bond, - (CH _{2) 1-3} -, - O-, or -NR ^'- (where, ^R' represents a hydrogen atom or an alkyl group.) a. ) divalent group represented by, or the general formula (Z2): - V-O -W- ( wherein (Z2) in, V is a single bond or - (CH _{2) 1-3} - and is, W is , Single bond,-(CH ₂ ) _1-3- , -C (= O)-, -S (O) _1-2- , or -C (= O) -NR ^' -(where R ^' is hydrogen Item 3. The compound according to item 1 or 2, which is a divalent group represented by the following group) which is an atom or an alkyl group: Wherein R ² is formula (Z1a): - S (O ) 1-2 -U- [ wherein, U is a single _{bond, - (CH 2) 1-3 -} , - O-, or -NR ^'- (However, R ^' shows a hydrogen atom or an alkyl group.). [Wherein W represents a single bond,-(CH ₂ ) _1-3- , -C (= O)-, -S], or a divalent group represented by the general formula (Z2a): -O-W- (O) _1-2 -, or ^{-C (= O) -NR '-} (. However, ^R' is represents a hydrogen atom or an alkyl group) is a divalent group represented by], section 1-3 The compound as described in any of the above.

Item 5. 5. The compound according to item 3 or 4, wherein R ² is —S (O) ₂ —.

Item 6. The compound according to any one of Items 1 to 5, wherein R ³ is a phenyl group which may be substituted.

Item 7. The compound represented by the general formula (1) is a compound represented by the general formula (1C):

[Wherein, R ¹¹ represents-(CHR ^11a- ) _n (n represents an integer of 1 to 3. R ^11a is the same or different and represents a hydrogen atom or an alkyl group, and when n is 2 or 3, two of them R ^11a may be bonded to each other to form a ring with the adjacent carbon atom. R ¹² and R ¹³ are the same or different and each represents a hydrogen atom or an alkyl group, and R ¹² and R ¹³ may be bonded to each other to form a ring with adjacent carbon atoms. R ¹⁴ represents a carbon or nitrogen atom. R ³¹ , R ³² , R ³³ , R ³⁴ , and R ³⁵ are the same or different and each is a hydrogen atom, a halogen atom, an alkyl group which may be substituted, an alkoxy group which may be substituted, or even substituted Good alkylthio group, alkenyl group which may be substituted, alkynyl group which may be substituted, amino group which may be substituted, nitro group, hydroxyl group, cyano group, -C (= O) R ³⁰¹ , -C (= O) OR ³⁰² , -C (= O) NR ³⁰³ R ³⁰⁴ , -S (= O) _1-2 R ³⁰⁵ , -S (= O) _1-2 NR ³⁰⁶ R ³⁰⁷
Indicates R ⁴ , R ⁵ and R ⁶ are the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group which may be substituted, an alkenyl group which may be substituted, or an alkynyl group which may be substituted. ]
7. The compound according to any one of Items 1 to 6, which is a compound represented by

Item 8. The above R ⁴ is an alkyl group which may be substituted, an alkenyl group which may be substituted, or an alkynyl group which may be substituted, and both of R ⁵ and R ⁶ may be hydrogen atoms. 7. The compound according to 7.

Item 9. General formula (1):

[Wherein, R ¹ represents a group derived from a hetero ring containing a nitrogen atom. R ² represents a divalent group which is a linker. R ³ represents an aryl group which may be substituted, a heteroaryl group which may be substituted, a cycloalkyl group which may be substituted, or an alkyl group having 1 to 6 carbon atoms. R ⁴ , R ⁵ and R ⁶ are the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group which may be substituted, an alkenyl group which may be substituted, or an alkynyl group which may be substituted. ]
A parasitic plant germination regulator containing a compound represented by the formula, or an agriculturally acceptable salt, hydrate or solvate thereof: Item 10. The germination regulator according to item 9, which is a parasitic plant germination inducer.

Item 11. 11. The germination regulator according to Item 9 or 10, wherein the parasitic plant is a Striga plant or an Orobanchi plant.

Item 12. Item 12. A method for controlling germination of a parasitic plant, which comprises applying the parasitic plant germination regulator according to any one of Items 9 to 11 to soil containing seeds of a parasitic plant.

According to the present invention, it is possible to provide a compound having parasitic plant germination regulatory activity (in particular, parasitic plant germination inducing activity), and a parasitic plant germination regulator using the compound. According to the present invention, or according to one aspect of the present invention, it is possible to provide a compound having a higher parasitic plant germination regulatory activity (in particular, a parasitic plant germination inducing activity) and a parasitic plant germination regulator. Moreover, according to the present invention, or according to one aspect of the present invention, a higher parasitic plant while reducing the influence on plants other than the parasitic plant (for example, crops in the soil where parasitic plant seeds are present). Germination control activity (especially, parasitic plant germination induction activity) can be exhibited. Furthermore, according to the present invention, or according to one aspect of the present invention, a compound having parasitic plant germination regulatory activity (in particular, parasitic plant germination inducing activity), and a parasitic plant germination regulator using the compound, It is also possible to provide inexpensively. Therefore, the use of the present invention is a practical striker countermeasure widely in the world, especially in countries and regions (especially in Africa, etc.) where countermeasures are not sufficiently implemented due to economic conditions etc. although the damage of strikers is serious. Can be taken.

In the present specification, the expressions "containing" and "including" include the concepts of "containing", "including", "consisting essentially of" and "consisting only of".

1. Compound According to one aspect of the present invention, a compound represented by the general formula (1):

[Wherein, R ¹ represents a group derived from a hetero ring containing a nitrogen atom. R ² represents a divalent group which is a linker. R ³ represents an aryl group which may be substituted, a heteroaryl group which may be substituted, a cycloalkyl group which may be substituted, or an alkyl group having 1 to 6 carbon atoms. R ⁴ , R ⁵ and R ⁶ are the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group which may be substituted, an alkenyl group which may be substituted, or an alkynyl group which may be substituted. ]
Or a agriculturally acceptable salt, hydrate or solvate thereof. This will be described below.

<1-1. About R ¹ >
The group derived from the heterocycle containing a nitrogen atom represented by R ¹ in the general formula (1) is not particularly limited as long as it is a divalent group obtained by removing hydrogen from the heterocycle. The heterocycle containing a nitrogen atom is not particularly limited as long as it is a ring (preferably non-aromatic) containing a nitrogen atom as a heteroatom, and examples thereof include pyrrolidine, piperidine, homopiperidine, imidazoline, piperazine, homopiperazine, morpholine and hexa Methyleneimine, pyrrole, pyrazole, thiazole, pyridine, pyrimidine, imidazole and the like; a ring formed by condensation of a hetero ring containing these nitrogen atoms and another hetero ring; a hetero ring and aromatic ring containing these nitrogen atoms (especially benzene ring) And a ring formed by condensation. The heterocycle is preferably a single ring. When the heterocycle containing a nitrogen atom is a polycycle, two bonds of R ¹ are preferably present in one of a plurality of rings constituting the polycycle. The number of ring members of the hetero ring is, for example, 3 to 10, preferably 4 to 8, more preferably 5 to 8, still more preferably 5 to 7, still more preferably 6 to 7, particularly preferably 6.

In the general formula (1), R ¹ is preferably a group represented by the general formula (Y):

[Wherein, R ¹¹ represents-(CHR ^11a- ) _n (n represents an integer of 1 to 3. R ^11a is the same or different and represents a hydrogen atom or an alkyl group, and when n is 2 or 3, two of them R ^11a may be bonded to each other to form a ring with the adjacent carbon atom. R ¹² and R ¹³ are the same or different and each represents a hydrogen atom or an alkyl group, and R ¹² and R ¹³ may be bonded to each other to form a ring with adjacent carbon atoms. R ¹⁴ represents a carbon or nitrogen atom. ]
And a divalent group represented by

In the general formula (Y), n is preferably 2 or 3, and more preferably 2.

In the general formula (Y), the alkyl group represented by R ^11a is any of linear, branched or cyclic (preferably linear or branched, more preferably linear) Is also included. The carbon number of the alkyl group is not particularly limited, and is, for example, 1 to 8, preferably 1 to 6, more preferably 1 to 4, further preferably 1 to 2, still more preferably 1. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, n-pentyl group, neopentyl group, n -Hexyl group, 3-methyl pentyl group and the like.

In the general formula (Y), when n is 1, preferred examples of R ^11a include a hydrogen atom. When n is 2 or 3, preferably, R ^11a is the same or different and is a hydrogen atom or an alkyl group, more preferably all of R ^11a are hydrogen atoms.

In the general formula (Y), the alkyl group represented by R ¹² or R ¹³ is linear, branched or cyclic (preferably linear or branched, more preferably linear). Both are included. The carbon number of the alkyl group is not particularly limited, and is, for example, 1 to 8, preferably 1 to 6, more preferably 1 to 4, further preferably 1 to 2, still more preferably 1. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, n-pentyl group, neopentyl group, n -Hexyl group, 3-methyl pentyl group and the like.

There is no particular limitation on the ring formed by two R ^11a 's bonded together to form an adjacent carbon atom, and the ring formed by R ¹² and R ¹³ together to form an adjacent carbon atom are not particularly limited; And rings, aliphatic rings such as cyclohexane, and heterocycles such as pyrimidine, pyridine, piperidine, pyran, thiophene and the like.

In general formula (Y), preferably, R ¹² and R ¹³ are the same or different and are a hydrogen atom or an alkyl group, and more preferably, R ¹² and R ¹³ are both a hydrogen atom.

In general formula (Y), R ¹⁴ is preferably a nitrogen atom.

In General Formula (1), as R ¹ , among divalent groups represented by General Formula (Y), more preferably General Formula (YA):

[Wherein, R ¹² and R ¹³ are as defined above. R ¹¹¹ and R ¹¹² are the same or different and each represents a hydrogen atom or an alkyl group, and R ¹¹¹ and R ¹¹² may be bonded to each other to form a ring with adjacent carbon atoms. ]
And a divalent group represented by

In the general formula (YA), the alkyl group represented by R ¹¹¹ or R ¹¹² is linear, branched or cyclic (preferably linear or branched, more preferably linear) Both are included. The carbon number of the alkyl group is not particularly limited, and is, for example, 1 to 8, preferably 1 to 6, more preferably 1 to 4, further preferably 1 to 2, still more preferably 1. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, n-pentyl group, neopentyl group, n -Hexyl group, 3-methyl pentyl group and the like.

In general formula (YA), preferably, R ¹¹¹ and R ¹¹² are the same or different and are a hydrogen atom or an alkyl group, more preferably R ¹¹¹ and R ¹¹² are both a hydrogen atom.

In the general formula (1), another preferable embodiment of R ¹ is a compound represented by general formula (Y ′)

[Wherein, R ¹⁵ represents a single bond or-(CHR ^15a- ) _m (m represents 1 or 2. R ^15a is the same or different and represents a hydrogen atom or an alkyl group, and when m is 2, adjacent 2 One R ^15a may be bonded to each other to form a ring with the adjacent carbon atom. R ¹⁶ and R ¹⁷ are the same or different and each represents a hydrogen atom or an alkyl group, and R ¹⁶ and R ¹⁷ may be bonded to each other to form a ring with adjacent carbon atoms. ]
And a divalent group represented by

In the general formula (Y ′), R ¹⁵ is preferably — (CHR ^15a —) _m .

In the general formula (Y ′), m is preferably 1.

In the general formula (Y ′), the alkyl group represented by R ^15a is the same as the alkyl group represented by R ^11a described above.

In the general formula (Y ′), the alkyl group represented by R ¹⁶ or R ¹⁷ is the same as the alkyl group represented by R ¹² or R ¹³ described above.

<1-2. About R ² >
The linker represented by R ² in the general formula (1) is not particularly limited as long as it is a divalent group that can function as a linker. As R ² , for example, in the general formula (Z1): -TU- (wherein T is -S (O) _1-2- , or -C (= O)-, or-(CH) _{2) 1-3} -, and, U is a single bond, - (CH _{2) 1-3} -, - O-, or -NR ^'-. a it) divalent group represented by,
Formula (Z2): - V-O -W- (In the formula (Z2), V represents a single bond or - (CH _{2) 1-3} - and is, W is a single bond, - (CH _{2) 1 -3 -, - C (= O} ) -, - S (O) 1-2 -, or ^{-C (= O) -NR '-} . a it) divalent group represented by and the like.

In the above definition, R ′ represents a hydrogen atom or an alkyl group. The alkyl group represented by R ′ is the same as the alkyl group represented by R ^11a above. Also, of the two bonds of R ² (bonds 1 and 2), bond 1 is to bond 2 and bonded to R ¹ may be attached to R ^3, or bond 1 R ³ And bond 2 may be attached to R ¹ .

In the general formula (Z1), T is preferably -S (O) _1-2- or -C (= O)-, more preferably -S (O) _1-2- .

In the general formula (Z1), U is preferably a single _{bond, - (CH 2) 1-3 -} , or -NR ^'-, more preferably an a single bond or -CH ₂ - are, furthermore preferably a single It is a bond.

Specifically as a bivalent group shown by general formula (Z1), the following groups etc. are mentioned, for example.

In general formula (Z2), V is preferably a single bond.

In the general formula (Z2), W is preferably-(CH ₂ ) _1-3- .

Specifically as a bivalent group shown by general formula (Z2), the following groups etc. are mentioned, for example.

In General Formula (1), as R ² , preferably, a divalent group represented by General Formula (Z1), a divalent group represented by General Formula (Z2) and the like can be mentioned.

Among the general formula (Z1), more preferably, the general formula (Z1a): -S (O) _1-2 -U- [wherein U is the same as the above. ] A divalent group, and the like represented, general formula further among (Z1a) preferably -S (O) _1-2 - include divalent groups represented by, more preferably more -S (O ₂ ) is mentioned.

Among the general formula (Z2), more preferably a general formula (Z2a): —O—W— wherein W is as defined above. And more preferably a divalent group represented by -O- (CH ₂ ) ₁ -3 among the general formula (Z2a), and still more preferably- Divalent groups represented by O- (CH ₂ )-can be mentioned.

<1-3. About R ³ >
The aryl group represented by R ³ in the general formula (1) is not particularly limited, but preferably has 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms, and still more preferably 6 to 8 carbon atoms. As such an aryl group, specifically, for example, phenyl group, naphthyl group, biphenyl group, pentarenyl group, indenyl group, anthranyl group, tetracenyl group, pentacenyl group, pyrenyl group, perylenyl group, fluorenyl group, phenanthryl group, etc. And preferably a phenyl group, a naphthyl group and the like, and more preferably a phenyl group and the like.

The substituent which the aryl group represented by R ³ may have in the general formula (1) is not particularly limited, and may be, for example, a halogen atom, an alkyl group which may be substituted, or a substituent An alkoxy group, an alkylthio group which may be substituted, an alkenyl group which may be substituted, an alkynyl group which may be substituted, an amino group which may be substituted, a nitro group, a hydroxyl group, a cyano group, -C ( = O) R ³⁰¹ , -C (= O) OR ³⁰² , -C (= O) NR ³⁰³ R ³⁰⁴ , -S (= O) _1-2 R ³⁰⁵ , -S (= O) _1-2 NR ³⁰⁶ R ^{No. 307 and the} like.

In the general formula (1), examples of the halogen atom which may be possessed by the aryl group represented by R ³ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

In the general formula (1), the alkyl group which may be substituted or substituted by the aryl group represented by R ³ is not particularly limited, and a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, Iodine atom etc.), oxo group, hydroxyl group, alkoxy group, amino group which may be substituted, phenyl group, etc. linear, branched or cyclic (preferably linear or branched) Branched, more preferably straight) alkyl groups having 1 to 8 carbon atoms, preferably 1 to 6, more preferably 1 to 5, more preferably 1 to 5, still more preferably 2 to 5, still more preferably 3 to 5 carbon atoms; Be The number of substituents is not particularly limited, and is, for example, 0 to 6, preferably 0 to 3, and more preferably 0. As such an alkyl group which may be substituted, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, perfluoro group A methyl group, a perfluoroethyl group etc. are mentioned.

The alkoxy group which may be substituted or substituted by the aryl group represented by R ³ in the general formula (1) is not particularly limited, and a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, Iodine atom etc.), oxo group, hydroxyl group, alkoxy group, amino group which may be substituted, phenyl group etc. linear or branched (preferably linear) carbon number of 1 There may be mentioned alkoxy groups of -8, preferably 1 to 6, more preferably 1 to 5, still more preferably 2 to 5, still more preferably 3 to 5. The number of substituents is not particularly limited, and is, for example, 0 to 6, preferably 0 to 3, and more preferably 0. As such an alkoxy group which may be substituted, for example, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, t-butoxy group, per And fluoromethoxy and perfluoroethoxy groups.

In the general formula (1), the alkylthio group which may be substituted or substituted by the aryl group represented by R ³ is not particularly limited, and a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, Iodine atom etc.), oxo group, hydroxyl group, alkoxy group, amino group which may be substituted, phenyl group etc. linear or branched (preferably linear) carbon number of 1 There may be mentioned -8, preferably 1 to 6, more preferably 1 to 4 alkylthio groups. The number of substituents is not particularly limited, and is, for example, 0 to 6, preferably 0 to 3. As such an optionally substituted alkylthio group, for example, methylthio group, ethylthio group, n-propylthio group, isopropylthio group, n-butylthio group, isobutylthio group, sec-butylthio group, t-butylthio group, Perfluoromethylthio group, perfluoroethylthio group and the like can be mentioned.

In the general formula (1), the optionally substituted alkenyl group which the aryl group represented by R ³ may have is not particularly limited, and a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, An iodine atom, etc.), an oxo group, a hydroxyl group, an alkoxy group, an amino group which may be substituted, a linear or branched chain (preferably linear) having 2 or more carbon atoms which may be substituted by a phenyl group etc. There may be mentioned -8, preferably 2 to 6, more preferably 2 to 4 alkenyl groups. The number of substituents is not particularly limited, and is, for example, 0 to 6, preferably 0 to 3. Examples of such alkenyl group which may be substituted include vinyl group, allyl group, 1-propenyl group, isopropenyl group, butenyl group, pentenyl group, hexenyl group and the like.

In the general formula (1), the optionally substituted alkynyl group which the aryl group represented by R ³ may have is not particularly limited, and a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, An iodine atom, etc.), an oxo group, a hydroxyl group, an alkoxy group, an amino group which may be substituted, a linear or branched chain (preferably linear) having 2 or more carbon atoms which may be substituted by a phenyl group etc. There may be mentioned -8, preferably 2-6, more preferably 2-4 alkynyl groups. The number of substituents is not particularly limited, and is, for example, 0 to 6, preferably 0 to 3. As such an optionally substituted alkynyl group, for example, ethynyl group, propynyl group (eg 1-propynyl group, 2-propynyl group (propargyl group)), butynyl group, pentynyl group, hexynyl group, phenylacetynyl group And the like.

There is no particular limitation on the optionally substituted amino group which the aryl group represented by R ³ may have in the general formula (1), and it may be linear or branched (preferably linear And C.-1), preferably 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and / or amino groups optionally substituted with an acyl group. The number of substitution by the alkyl group and / or the acyl group is preferably 1 to 2 (when the substituent is an alkyl group and / or an acyl group and the number of substitutions is 2, the alkyl group and / or the acyl group are linked And the adjacent nitrogen atom may form a ring). As such an amino group which may be substituted, an amino group, a methylamino group, an ethylamino group, a dimethylamino group, a diethylamino group, an ethylmethylamino group, an acetamide group etc. are mentioned, for example.

The substituent which the aryl group represented by R ³ may have in the general formula (1) is preferably a halogen atom, an alkyl group which may be substituted, an alkoxy group which may be substituted, a substituent And alkylthio groups which may be substituted, alkenyl groups which may be substituted, alkynyl groups which may be substituted, amino groups which may be substituted, nitro groups and the like, and more preferably a halogen atom or substituted Examples thereof include an alkyl group which may be substituted, an alkoxy group which may be substituted, a nitro group and the like, and more preferably an alkyl group which may be substituted and an alkoxy group which may be substituted and the like.

R ³⁰¹ , R ³⁰² , R ³⁰³ , R ³⁰⁴ , R ³⁰⁵ , R ³⁰⁶ and R ³⁰⁷ each represent a hydrogen atom, an alkyl group which may be substituted, or a phenyl group which may be substituted. The definitions of the “optionally substituted alkyl group” and the “optionally substituted phenyl group” are the same as the definitions of the substituent which the aryl group represented by R ³ may have. is there.

The number of substituents of the aryl group represented by R ³ in the general formula (1) is, for example, 0 to 5, preferably 1 to 3, and more preferably 1.

The heteroaryl group represented by R ³ in the general formula (1) is not particularly limited, but preferably has 5 to 20 ring atoms, more preferably 5 to 12 and still more preferably 5 to 8 ring atoms. Particularly preferred. As such a heteroaryl group, specifically, for example, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, thienyl group, furyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, oxazolyl group, thiazolyl group, isoxazolyl group And isothiazolyl group, indolyl group, quinolyl group and the like.

In the general formula (1), for the heteroaryl group substituent which may be possessed represented by R ^3, the same as the substituent which the aryl group may be possessed by R ³ described above.

The cycloalkyl group represented by R ³ in the general formula (1) is not particularly limited, and is, for example, a cycloalkyl group having a carbon number of 3 to 8, preferably 4 to 7, more preferably 5 to 7, and still more preferably 6 Can be mentioned. As such a cycloalkyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group etc. are mentioned, for example.

In the general formula (1), the cycloalkyl group substituent which may be possessed represented by R ^3, the same as the substituent which the aryl group may be possessed by R ³ described above.

In the general formula (1), the alkyl group having 1 to 6 carbon atoms represented by R ³ is not particularly limited. Examples of such an alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and t-butyl group.

In the general formula (1), for the substituent that the alkyl group have 1 to 6 carbon atoms represented by R ^3, the above-mentioned R ³ aryl groups include optionally substituent group represented by Is the same as

In the general formula (1), preferred examples of R ³ include an aryl group which may be substituted, and more preferably a general formula (X):

[Wherein, R ³¹ , R ³² , R ³³ , R ³⁴ and R ³⁵ are the same or different and are a hydrogen atom, a halogen atom, an alkyl group which may be substituted, an alkoxy group which may be substituted, a substitution Alkylthio group which may be substituted, alkenyl group which may be substituted, alkynyl group which may be substituted, amino group which may be substituted, nitro group, hydroxyl group, cyano group, -C (= O) R ³⁰¹ , -C (= O) OR ³⁰² , -C (= O) NR ³⁰³ R ³⁰⁴ , -S (= O) _1-2 R ³⁰⁵ , -S (= O) _1-2 , or NR ³⁰⁶ R ³⁰⁷ Show. Indicates ]
And a group represented by

In the general formula ^{(X), R 31, R} 32, R 33, R 34, or for various substituents represented by R ³⁵ represents a substituent which may be aryl groups have represented by R ³ described above It is similar.

In the general formula (X), preferably 1 to 3 (preferably 1 or more preferably R ³¹ ) of R ³¹ , R ³² , R ³³ , R ³⁴ and R ³⁵ is a halogen atom or substituted An alkyl group which may be substituted, an alkoxy group which may be substituted, or a nitro group, and all the others are hydrogen atoms, more preferably an alkyl group which R ³¹ may be substituted, even if it is substituted. And R ³² , R ³³ , R ³⁴ and R ³⁵ are all hydrogen atoms.

<1-4. About R ⁴ , R ⁵ , and R ⁶ >
As a halogen atom shown by R < ⁴ >, R < ⁵ > or R < ⁶ > in General formula (1), a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned.

In the general formula (1), the optionally substituted alkyl group represented by R ⁴ , R ⁵ or R ⁶ is not particularly limited, and a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. ), Oxo group, hydroxyl group, alkoxy group, amino group which may be substituted, linear, branched or cyclic (preferably linear or branched) which may be substituted by phenyl group etc. More preferably, it is an alkyl group having 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, still more preferably 1 to 3 carbon atoms, and still more preferably 1 to 2 carbon atoms. The number of substituents is not particularly limited, and is, for example, 0 to 6, preferably 0 to 3, and more preferably 0. As such an alkyl group which may be substituted, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, perfluoro group A methyl group, a perfluoroethyl group etc. are mentioned.

In the general formula (1), the optionally substituted alkenyl group represented by R ⁴ , R ⁵ or R ⁶ is not particularly limited, and a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. ), An oxo group, a hydroxyl group, an alkoxy group, an amino group which may be substituted, a linear or branched chain (preferably linear) having 2 to 8 carbon atoms which may be substituted by a phenyl group or the like; Preferably, 2 to 6, more preferably 2 to 4 alkenyl groups can be mentioned. The number of substituents is not particularly limited, and is, for example, 0 to 6, preferably 0 to 3, and more preferably 0. Examples of such alkenyl group which may be substituted include vinyl group, allyl group, 1-propenyl group, isopropenyl group, butenyl group, pentenyl group, hexenyl group and the like.

In the general formula (1), the optionally substituted alkynyl group represented by R ⁴ , R ⁵ or R ⁶ is not particularly limited, and a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. ), An oxo group, a hydroxyl group, an alkoxy group, an amino group which may be substituted, a linear or branched chain (preferably linear) having 2 to 8 carbon atoms which may be substituted by a phenyl group or the like; Preferably, 2 to 6, and more preferably 2 to 4 alkynyl groups can be mentioned. The number of substituents is not particularly limited, and is, for example, 0 to 6, preferably 0 to 3, and more preferably 0. As such an optionally substituted alkynyl group, for example, ethynyl group, propynyl group (eg 1-propynyl group, 2-propynyl group (propargyl group)), butynyl group, pentynyl group, hexynyl group, phenylacetynyl group And the like.

In the general formula (1), R ⁴ is preferably a hydrogen atom, an alkyl group which may be substituted, an alkenyl group which may be substituted, an alkynyl group which may be substituted, etc., and more preferably Is a hydrogen atom, an alkyl group which may be substituted, an alkenyl group which may be substituted, etc., more preferably an alkyl group which may be substituted, an alkenyl group which may be substituted, etc. .

In the general formula (1), preferred examples of R ⁵ include a hydrogen atom, an alkyl group which may be substituted, an alkenyl group which may be substituted, an alkynyl group which may be substituted and the like, and more preferred. Is a hydrogen atom.

In the general formula (1), R ⁶ preferably includes a hydrogen atom, an alkyl group which may be substituted, an alkenyl group which may be substituted, an alkynyl group which may be substituted, etc., and more preferably Is a hydrogen atom.

In one aspect, R ⁴ is an alkyl group which may be substituted, an alkenyl group which may be substituted, or an alkynyl group which may be substituted, and both of R ⁵ and R ⁶ are a hydrogen atom. Is preferred.

<1-5. Preferred General Formula>
In one aspect of the present invention, the compound represented by the general formula (1) is preferably a compound represented by the general formula (1A):

[Wherein, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ are as defined above. ]
And the compounds represented by the general formula (1B) are more preferable.

[Wherein, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ³ , R ⁴ , R ⁵ , and R ⁶ are as defined above. ]
And the compounds represented by the general formula (1C) are more preferable.

[Wherein, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ⁴ , R ⁵ , and R ⁶ are as defined above. ]
And more preferably compounds represented by general formula (1D):

[Wherein, R ¹¹ , R ¹² , R ¹³ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ⁴ , R ⁵ and R ⁶ are as defined above. ]
The compound represented by these is mentioned.

<1-6. Salt, Hydrate, Solvate>
The salt of the compound represented by the general formula (1) is not particularly limited as long as it is an agriculturally acceptable salt. As the salt, either an acid salt or a basic salt can be employed. Examples of the acid salt include mineral acid salts such as hydrochloride, hydrobromide, sulfate, nitrate, and phosphate; acetate, propionate, tartrate, fumarate, maleate, malic acid Organic acid salts such as salts, citrates, methanesulphonates, paratoluenesulphonates, etc. Examples of basic salts include alkali salts such as sodium salts and potassium salts; and calcium salts, magnesium Alkaline earth metal salts such as salts; salts with ammonia; morpholine, piperidine, pyrrolidine, monoalkylamine, dialkylamine, trialkylamine, mono (hydroxyalkyl) amine, di (hydroxyalkyl) amine, tri (hydroxyalkyl) Examples thereof include salts with organic amines such as amines.

The compound represented by the general formula (1) can also be a hydrate or a solvate. Examples of the solvent include agriculturally acceptable organic solvents (eg, ethanol, glycerol, acetic acid, etc.) and the like.

2. Production Method The compound represented by the general formula (1) can be synthesized by various methods.

2-1. Manufacturing method 1
The compound represented by the general formula (1) is, for example, the following reaction formula:

[Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are as defined above. X is a leaving group (for example, a halogen atom, an imidazolyl group, an alkoxy group, an acyloxy group etc., preferably a halogen atom, preferably a chlorine atom). ]
Can be synthesized according to or in a similar manner.

In this reaction, the compound represented by General Formula (1) can be obtained by reacting the compound represented by General Formula (1a) with the compound represented by General Formula (1b).

The amount of the compound represented by the general formula (1a) is preferably 0.5 to 10 moles, generally 1.5 to 6 moles, per mole of the compound represented by the general formula (1b), from the viewpoint of yield etc The mole is more preferable, and 2 to 4 moles are more preferable.

The reaction is preferably carried out in the presence of a catalyst. The catalyst is not particularly limited, and examples thereof include base catalysts such as N, N-dimethyl-4-aminopyridine (DMAP), triethylamine (Et ₃ N) and the like. The catalyst may be used alone or in combination of two or more.

The amount of the catalyst used varies depending on the type of the catalyst, but is, for example, about 0.1 to 10 moles relative to 1 mole of the compound represented by the general formula (1a).

The reaction is usually carried out in the presence of a reaction solvent. The reaction solvent is not particularly limited, and examples thereof include dichloromethane, acetonitrile, tetrahydrofuran, acetone, toluene and the like, with preference given to dichloromethane and the like. The solvents may be used alone or in combination of two or more.

In the present reaction, in addition to the above components, additives may be appropriately used as long as the progress of the reaction is not significantly impaired.

The reaction can be carried out under heating, at normal temperature or under cooling, and usually carried out at 0 to 50 ° C. (particularly 0 to 30 ° C.). The reaction time is not particularly limited, and can usually be 4 hours to 48 hours, particularly 8 hours to 24 hours.

The progress of the reaction can be followed by conventional methods such as chromatography. After completion of the reaction, the solvent is distilled off, and the product can be isolated and purified by a usual method such as chromatography or recrystallization. Further, the structure of the product can be identified by elemental analysis, MS (ESI-MS) analysis, IR analysis, ¹ H-NMR, ¹³ C-NMR or the like.

2-2. Manufacturing method 2
The compound represented by the general formula (1) is, for example, the following reaction formula:

[Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are as defined above. X is a leaving group (for example, a halogen atom, an imidazolyl group, an alkoxy group, an acyloxy group etc., preferably a halogen atom, preferably a chlorine atom). ]
Can be synthesized according to or in a similar manner.

In this reaction, the compound represented by General Formula (1) can be obtained by reacting the compound represented by General Formula (1c) with the compound represented by General Formula (1d).

The reaction conditions and the like of this reaction are the same as the reaction conditions and the like described in the above-mentioned "2-1. Production method 1".

3. The compound represented by the general formula (1) has a parasitic plant germination regulatory action (in particular, a parasitic plant germination inducing action). Accordingly, the compound represented by the general formula (1) or a salt, hydrate or solvate thereof can be used as an active ingredient of a parasitic plant germination regulator (in particular, a parasitic plant germination inducer).

If, for example, a parasitic plant germination regulator is applied under an environment where there is no plant serving as a host of the parasitic plant, the germinated parasitic plant will not be able to infest, and the soil may be cleaned. .

There is no restriction | limiting in particular as a plant used as the host of a parasitic plant, For example, corn, millet, sorghum, sugarcane, rice, a bean etc. are mentioned.

The parasitic plants to be targeted are not particularly limited, and typically include Striga plants. Examples of Striga plants include Striga hermonthica, Striga gesnerioides, Striga asiatica, Striga aequinoctialis, Striga angolensis, Striga angustifolia, Striga aspera, Striga bilbiiata, Striga chrysantha, Striga chil Striga gracillima, Striga hallaei, Striga hirsuta, Striga jundii, Striga klingii, Striga latericea, Striga lepidagathidis, Striga lutea, Striga macrantha, Striga pinargifei, Striga primuloides, Striga pubiflora, Striga pπflora etc. In addition, as parasitic plants targeted by the present invention, for example, Orobanchi plants, Felipanchi plants, Alektra plants and the like can be mentioned. As an Orobanchi plant, for example, Orobanche cernua, Orobanche crenata, Orobanche cumana, Orobanche foetida, Orobanche minor etc., as a Felipanchi genus plant, for example, Phelipanche aegyptiaca, Phelipanche ramosa etc, as an Alextra plant, for example, Alectra orobanidoes Alectra sessiliflora, Alectra vogelii. The parasitic plants to be targeted preferably include Striga plants, Orobanchi plants, and Feripanchi plants, more preferably Striga plants and Orobanchi plants, and further preferably Striga hermonthica and Orobanche minor.

The parasitic plant germination regulator of the present invention may consist only of the active ingredient (the compound represented by the general formula (1), or a salt, hydrate or solvate thereof), but in addition to these, an agent Various additives may be included depending on the form, application mode and the like. The content ratio of the active ingredient in the agent of the present invention is not particularly limited. Specifically, about 0.0001 to 100% by weight, preferably about 0.01 to 50% by weight is exemplified.

The dosage form of the parasitic plant germination regulator of the present invention is not particularly limited as long as it is an agriculturally acceptable dosage form. For example, solutions, solids, powders, granules, granules, wettable powders, flowables, emulsions, pastes, dispersants and the like can be mentioned.

The additive is not particularly limited as long as it is an agriculturally acceptable additive. For example, carriers, surfactants, thickeners, extenders, binders, vitamins, antioxidants, pH adjusters, volatilization inhibitors, pigments and the like can be mentioned.

The application mode of the parasitic plant germination regulator of the present invention is not particularly limited as long as it is an aspect in which the above-mentioned active ingredient and parasitic plant seed can be in contact. For example, the aspect which spreads, drips, applies, mixes etc. the agent of this invention to the soil containing a parasitic plant seed is mentioned.

Hereinafter, the present invention will be described in detail based on examples, but the present invention is not limited by these examples.

Example 1 Synthesis of compounds Compounds represented by the following formula (6R) (compounds 1 to 9), compounds represented by the following formula (7R) (compounds 10 to 21), compounds represented by the following formula (8AB) (compound 22) To 26), compounds represented by the following formula (9AB) (compounds 27 to 28), compounds represented by the following formula (10AB) (compounds 29 to 30), and the following compound 31 were synthesized.

<Synthesis of Compound 1>
Compound 1 was synthesized according to the following synthesis scheme. In the synthesis scheme, Et represents an ethyl group (the same applies to the following schemes).

Step: 1
4-butoxybenzene-1-sulfonyl chloride (RX) (1a) (1.36 g, 5.5 mmol, 1 equiv.) In a solution of piperazine (2a) (1.86 g, 22 mmol, 4 equiv.) In dichloromethane (55 mL) And triethylamine (1.2 mL, 8.25 mmol, 1.5 equiv.) Were added and stirred at room temperature overnight, and then quenched with saturated sodium bicarbonate. The reaction mixture was extracted (x 3) with dichloromethane (10 mL) and dried over anhydrous Na ₂ SO ₄ . After the solvent was evaporated, the residue was purified by silica gel column (eluent: mixed solvent of chloroform / methanol) to obtain amine (3) as white solid (1.52 g, yield 93%).

Step: 2
A solution of triphosgene (0.15 g, 0.50 mmol, 1 equiv.) In dichloromethane (1.9 mL) is cooled to 0 ° C. and amine (3) (0.15 g, 0.50 mmol, 1 equiv.) And triethylamine (0.2 mL, 1.50 mmol) , 3 equiv.) Was added and stirred for 2 hours under argon atmosphere. While maintaining the reaction solution at 0 ° C, dichloromethane (5 mL), 5-hydroxy-3-methyl-2-furanone (4a) (0.17 g, 1.5 mmol, 3 equiv.), Triethylamine (0.2 mL, 1.50 mmol, 3 equiv., And N, N-dimethyl-4-aminopyridine (6.1 mg, 0.05 mmol, 10 mol%) were added, and the reaction was stirred overnight while slowly returning to room temperature. The reaction was quenched with saturated sodium bicarbonate, extracted (x 3) with dichloromethane (5 mL) and dried over anhydrous Na ₂ SO ₄ . The solvent was evaporated and then the residue was purified by silica gel column (eluent: mixed solvent of hexane / ethyl acetate) to obtain white solid target compound (5) (compound 1) (0.19 g, yield 87%) ).
¹ H NMR (600 MHz, CDCl ₃ ) δ 7.65 (2 H, dt, J = 9.0, 1.8 Hz), 6.99 (2 H, dt, J = 9.0, 1.8 Hz), 6.85-6.83 (1 H, m), 6.83- 6.82 (1 H, m), 4.03 (2 H, t, J = 6.0 Hz), 3. 76 (1 H, d, J = 12.0 Hz), 3. 65 (1 H, d, J = 12.0 Hz), 3. 47 (1 H, t, J = 10.2 Hz), 3.43 (1 H, t, J = 10.2 Hz), 3. 19 (1 H, br), 3. 12 (1 H, br), 2. 84 (1 H, t, J = 10.2 Hz), 2. 79 (1 H, t, J = 10.2 Hz), 1.97 (3 H, s), 1. 80 (2 H, td, J = 7.2, 6.0 Hz), 1.51 (2 H, sextet, J = 7.2 Hz), 0.99 (3 H, t, J = 7.2 Hz); ¹³ C NMR (151 MHz, CDCl ₃ ) δ 171.1, 163.2, 152.4, 142.1, 130.0, 126.4, 115.0, 93.9, 68.4, 45.8, 43.7, 43.4, 31.2, 19.3, 14.0, 10.8, one carbon atom was not found due to overlapping; IR (film) 2940, 2872, 1776, 1717, 1593, 1435, 1346, 1242, 1159, 1095, 955, 930 cm- ¹ ; HRMS (ESI) Calcd for C ₂₀ H ₂₆ O _{7 ^{N 2 NaS + ([M +}} Na] +) 461.1353, Found 461.1356.

<Synthesis of Compounds 2 to 26>
According to the synthesis method of Compound 1, it was synthesized using appropriate material compounds.

[Compound 2] White solid (145 mg, 73% yield). ¹ H NMR (600 MHz, CDCl ₃ ) δ 7.67 (2 H, d, J = 8.4 Hz), 7.01 (2 H, d, J = 8.4 Hz), 6.85-6.84 (1 H, m), 6.83 (1 H, brs) , 3.89 (3H, s), 3.77 (1H, brd, J = 12.2 Hz), 3.66 (1H, brd, J = 12.2 Hz), 3.52-3.40 (2H, m), 3.19 (1H, brs), 3.13 (3H) 1 H, brs), 2. 84 (1 H, t, J = 8.4 Hz), 2. 79 (1 H, t, J = 8.4 Hz), 1. 97 (3 H, s); ¹³ C NMR (151 MHz, CDCl ₃ ) δ 171.1, 163.4 IR (film) 2895, 2855, 1805, 1780, 1717, 1595, 1435, 152.3, 142.1, 134.4, 126.6, 114.5, 93.7, 55.7, 45.7, 43.5, 43.3, 10.6, one carbon atom was not found due to overlapping; , 1346, 1242, 1192, 1061 , 1016, 955 cm -1; HRMS (ESI) Calcd for C 17 H 20 O 7 N 2 NaS + ([M + Na] +) 419.0883, Found 419.0871.

Compound 3 white solid (57 mg, 82% yield). ¹ H NMR (600 MHz, CDCl ₃ ) δ 7.66 (2 H, dt, J = 9.0, 1.8 Hz), 6.99 (2 H, dt, J = 9.0, 1.8 Hz), 6.85 (1 H, m), 6.82 (1 H, m), 4.11 (2H, q, J = 6.9 Hz), 3.75 (1 H, d, J = 11.4 Hz), 3.65 (1 H, d, J = 11.4 Hz), 3.48 (1 H, t, J = 9.0 Hz) , 3.44 (1 H, t, J = 9.0 Hz), 3.18 (1 H, br), 3. 12 (1 H, br), 2. 84 (1 H, t, J = 9.0 Hz), 2.80 (1 H, t, J = 9.0 Hz) , 1.96 (3H, s), 1.45 (3H, t, J = 6.9 Hz); ¹³ C NMR (151 MHz, CDCl ₃ ) δ 171.2, 163.0, 152.4, 142.1, 134.6, 129.9, 126.4, 115.0, 93.8, 64.2 , 45.8, 43.6, 43.4, 14.7, 10.7, one carbon atom was not found due to overlapping; IR (film) 2899, 1780, 1713, 1595, 1420, 1329, 1260, 1207, 1092, 1015, 955 cm- ¹ ; _{HRMS (ESI) Calcd for C 18} H 22 O 7 N 2 NaS + ([M + Na] +) 433.1040, Found 433.1039.

[Compound 4] white solid (145 mg, yield 68%). ¹ H NMR (600 MHz, CDCl ₃ ) δ 7.66 (2 H, d, J = 9.0 Hz), 7.00 (2 H, d, J = 9.0 Hz), 6.85 (1 H, s), 6.83 (1 H, s), 3.99 (2H, t, J = 7.2 Hz), 3.76 (1 H, d, J = 12.6 Hz), 3.66 (1 H, d, J = 12.6 Hz), 3.48 (1 H, t, J = 9.6 Hz), 3.44 (1 H , t, J = 9.6 Hz), 3. 18 (1 H, br), 3. 12 (1 H, br), 2. 84 (1 H, t, J = 9.6 Hz), 2. 79 (1 H, t, J = 9.6 Hz), 1. 97 (3 H) , s), 1.85 (2 H, sextet, J = 7.2 Hz), 1.06 (3 H, t, J = 7.2 Hz); ¹³ C NMR (151 MHz, CDCl ₃ ) δ 171.2, 163.2, 152.4, 142.1, 134.7, 130.0 , 126.4, 115.0, 93.9, 70.2, 43.8, 43.4, 22.5, 10.8, 10.6, one carbon atom was not found due to overlapping; IR (film) 2941, 2899, 1775, 1707, 1591, 1439, 1244, 1242 , 1159, 1092, 1011, 955, 934 cm ^-1 ; HRMS (ESI) Calcd for C ₁₉ H ₂₄ O ₇ N ₂ NaS ⁺ ([M + Na] ⁺ ) 447.1196, Found 447.1195.

[Compound 5] White solid (230 mg, yield 99%). ¹ H NMR (600 MHz, CDCl ₃ ) δ 7.65 (2 H, d, J = 8.4 Hz), 6.99 (2 H, d, J = 8.4 Hz), 6. 85 (1 H, brs), 6.82 (1 H, brs), 4.02 (2H, t, J = 7.0 Hz), 3. 76 (1 H, d, J = 12.6 Hz), 3. 66 (1 H, d, J = 12.6 Hz), 3. 48 (1 H, t, J = 9.0 Hz), 3. 44 (1 H , t, J = 9.0 Hz), 3. 18 (1 H, br), 3. 12 (1 H, br), 2. 84 (1 H, t, J = 9.0 Hz), 2. 79 (1 H, t, J = 9.0 Hz), 1. 96 (3 H) , s), 1.82 (2 H, quintet, J = 7.0 Hz), 1. 45 (2 H, quintet, J = 7.0 Hz), 1. 40 (2 H, sextet, J = 7.0 Hz), 0.94 (3 H, t, J = 7.0 Hz) ¹³ C NMR (151 MHz, CDCl ₃ ) δ 171.2, 163.2, 152.4, 144.6, 129.9, 126.4, 115.0, 93.8, 68.7, 45.8, 43.6, 43.4, 28.8, 28.2, 22.5, 14.1, 10.7, one) HRMS (ESI) Calcd for C ₂₁ H ₂₈ carbon atom was not found due to overlapping; IR (film) 2936, 2922, 1769, 1722, 1595, 1433, 1348, 1422, 1165, 1092, 1015, 957 cm ^-1 ; HRMS (ESI) O ₇ N ₂ NaS ⁺ ([M + Na] ⁺ ) 475.1509, Found 475.1507.

[Compound 6] White solid (130 mg, yield 66%). ¹ H NMR (600 MHz, CDCl ₃ ) δ 7.64 (2 H, d, J = 8.4 Hz), 7. 37 (2 H, d, J = 8.4 Hz), 6. 84 (1 H, quintet, J = 1.2 Hz), 6.82 (1 H , quintet, J = 1.2 Hz, 3.77 (1 H, d, J = 12.3 Hz), 3. 67 (1 H, d, J = 12.3 Hz), 3. 47 (1 H, t, J = 11.4 Hz), 3.43 (1 H, t , J = 11.4 Hz), 3.21 (1 H, t, J = 6.6 Hz), 3. 15 (1 H, t, J = 6.6 Hz), 2. 85 (1 H, t, J = 8.8 Hz), 2. 80 (1 H, t, J = 8.8 Hz), 2.75 (2 H, q, J = 7.8 Hz), 1. 96 (3 H, t, J = 1.2 Hz), 1. 29 (3 H, t, J = 7.8 Hz); ¹³ C NMR (151 MHz, CDCl ₃₎ 5) 171.1, 152.4, 150.5, 142.1, 132.5, 128.9, 128.0, 93.9, 45.8, 43.5, 29.0, 15.2, 10.8, one carbon atom was not found due to overlapping; IR (film) 2967, 2926, HRCS (ESI) Calcd for C ₁₈ H ₂₂ O ₆ N ₂ NaS ⁺ ([M + Na] ⁺ ) 417.1.1091 2855, 1778, 1719, 1435, 1342, 1125, 1015, 928 cm ^-1 ; , Found 417.1089.

[Compound 7] White solid (220 mg, yield 99%). ¹ H NMR (600 MHz, CDCl ₃ ) δ 7.63 (2 H, d, J = 8.4 Hz), 7. 35 (2 H, d, J = 8.4 Hz), 6. 84 (1 H, brs), 6.83 (1 H, s), 3.77 (1H, d, J = 12.3 Hz), 3.67 (1 H, d, J = 12.3 Hz), 3.48 (1 H, t, J = 9.6 Hz), 3.44 (1 H, t, J = 9.6 Hz), 3.21 (1 H , t, J = 6.0 Hz), 3.15 (1 H, t, J = 6.0 Hz), 2. 86 (1 H, t, J = 8.4 Hz), 2.81 (1 H, t, J = 8.4 Hz), 2. 68 (2 H, t) , J = 7.2 Hz), 1.96 (3 H, s), 1. 65 (2 H, quintet, J = 7.2 Hz), 1.39-1.30 (4 H, m), 0.91 (3 H, t, J = 7.2 Hz); ¹³ C NMR _{(151 MHz, CDCl 3) δ} 171.1, 152.4, 149.3, 142.1, 134.7, 132.5, 129.4, 127.9, 93.9, 45.8, 43.7, 43.5, 36.0, 31.6, 30.8, 22.6, 10.8, one carbon atom was not found due to overlapping (IR) 2928, 2857, 1780, 1721, 1435, 1350, 1242, 1126, 1126, 1092, 1055, 955 cm- ¹ ; HRMS (ESI) Calcd for C ₂₁ H ₂₈ O ₆ N ₂ NaS ⁺ ( [M + Na] ^< +>) 459.1560, Found 459.1558.

Compound 8 white solid (220 mg, yield 99%). ¹ H NMR (600 MHz, CDCl ₃ ) δ 7.88 (2 H, d, J = 8.2 Hz), 7.84 (2 H, d, J = 8.2 Hz), 6.84 (1 H, brs), 6.83 (1 H, brs), 3.77 (1H, d, J = 12.0 Hz), 3.68 (1 H, d, J = 12.0 Hz), 3.52 (1 H, t, J = 10.2 Hz), 3.48 (1 H, t, J = 10.2 Hz), 3.23 (1 H , br), 3.17 (1 H, br), 2. 95 (1 H, t, J = 10.2 Hz), 2. 90 (1 H, t, J = 10.2 Hz), 1. 97 (3 H, s); ¹³ C NMR (151 MHz, CDCl ₃ ) δ 171.1, 152.4, 142.0, 135.2, 135.2 (q, J _CF = 33.2 Hz), 134.8, 128.3, 126.7 (q, J _CF = 4.2 Hz), 123.2 (q, J _CF = 273.2 Hz), 93.9, IR (film) 2928, 2859, 1780, 1721, 1437, 1323, 1244, 1171, 1128, 1063, 1015, 955 cm- ¹ ; HRMS 45.7, 43.7, 43.4, 10.8, one carbon atom was not found due to overlapping; _{(ESI) Calcd for C 17 H} 17 O 6 N 2 F 3 NaS + ([M + Na] +) 457.0652, Found 457.0646.

[Compound 9] White solid (37 mg, yield 83%). ¹ H NMR (600 MHz, CDCl ₃ ) δ 7.89-7.87 (1 H, m), 7.77 (1 H, d, J = 8.2 Hz), 7.67 (1 H, d, J = 8.2 Hz), 7.44 (1 H, t, J = 8.2 Hz), 6.86-6.84 (1 H, m), 6.82 (1 H, brs), 3. 75 (1 H, d, J = 12.6 Hz), 3.65 (1 H, d, J = 12.6 Hz), 3.52 (1 H, t, J = 11.4 Hz), 3.47 (1 H, t, J = 11.4 Hz), 3. 20 (1 H, brs), 3. 13 (1 H, brs), 2. 94 (1 H, t, J = 7.0 Hz), 2. 89 (1 H, t, J = 7.0 Hz), 1.97 (3 H, s); ¹³ C NMR (151 MHz, CDCl ₃ ) δ 171.1, 152.4, 142.0, 137.4, 136.5, 131.0, 130.6, 126.3, 123.6, 93.9, 45.8, IR (film) 2924, 2862, 1776, 1717, 1435, 1352, 1240, 1169, 1125, 1096, 1015, 953 cm- ¹ ; HRMS (ESIS ESI, 43.7, 43.4, 10.8, one carbon atom was not found due to overlapping; ) Calcd for C ₁₆ H ₁₇ O ₆ N ₂ ⁷⁹ BrNaS ⁺ ([M + Na] ⁺ ) 466.9883, Found 466.9876.

Compound 10 white solid (21 mg, 55% yield). ¹ H NMR (600 MHz, CDCl ₃ ) δ 7.68 (2 H, dt, J = 9.0, 2.4 Hz), 7.27 (1 H, dd, J = 7.2, 1.8 Hz), 7.02 (2 H, dt, J = 9.0, 2.4 Hz), 6.96 (1 H, t, J = 1.8 Hz), 6. 29 (1 H, d, J = 7.2 Hz), 3. 89 (3 H, s), 3. 77 (1 H, d, J = 12.6 Hz), 3. 67 (1 H, d, J = 12.6 Hz), 3.49 (1 H, t, J = 11.0 Hz), 3. 45 (1 H, t, J = 11.0 Hz), 3. 20 (1 H, br), 3. 14 (1 H, br), 2. 85 (1 H, t, J = 11.0 Hz), 2.81 (1 H, t, J = 11.0 Hz); ¹³ C NMR (151 MHz, CDCl ₃ ) δ 169.7, 163.6, 152.2, 149.7, 130.0, 126.8, 125.5, 114.7, 95.4, 55.8 , 45.8, 43.7, 43.5, one carbon atom was not found due to overlapping; IR (film) 2982, 2847, 1792, 1719, 1595, 1495, 1437, 1348, 1242, 1161, 1092, 1018, 926 cm- ¹ ; _{HRMS (ESI) Calcd for C 16} H 18 O 7 N 2 NaS + ([M + Na] +) 405.0727, Found 405.0721.

[Compound 11] White solid (38 mg, yield 56%). ¹ H NMR (600 MHz, CDCl ₃ ) δ 7.66 (2 H, dt, J = 8.7, 2.4 Hz), 7.27 (1 H, dd, J = 5.4, 1.2 Hz), 6.99 (2 H, dt, J = 8.7, 2.4 Hz), 6.96 (1 H, t, J = 1.2 Hz), 6. 29 (1 H, dd, J = 5.4, 1.2 Hz), 4.11 (2 H, q, J = 7.5 Hz), 3.77 (1 H, d, J = 12.6) Hz), 3.67 (1H, d, J = 12.6 Hz), 3.49 (1 H, t, J = 10.5 Hz), 3.45 (1 H, t, J = 10.5 Hz), 3.19 (1 H, brs), 3.13 (1 H, brs), 2.85 (1 H, t, J = 10.5 Hz), 2. 80 (1 H, t, J = 10.5 Hz), 1.57 (3 H, s), 1. 46 (3 H, t, J = 7.5 Hz); ¹³ C NMR ( 151 MHz, CDCl ₃ ) δ 169.7, 163.0, 152.2, 140.0, 126.5, 125.5, 115.0, 95.4, 64.2, 45.8, 43.5, 14.8, one carbon atom was not found due to overlapping; IR (film) 2984 , 1792, 1717, 1595, 1435, 1348, 1242, 1161, 1090, 1018, 924 cm ^-1 ; HRMS (ESI) Calcd for C ₁₇ H ₂₀ O ₇ N ₂ NaS ⁺ ([M + Na] ⁺ ) 419.9083, Found 419.0877.

[Compound 12] White solid (137 mg, yield 67%). ¹ H NMR (600 MHz, CDCl ₃ ) δ 7.66 (2 H, d, J = 8.7 Hz), 7.28 (1 H, dd, J = 6.0, 1.2 Hz), 7.00 (2 H, d, J = 8.7 Hz), 6.96 (1H, t, J = 1.2 Hz), 6.29 (1 H, dd, J = 6.0, 1.2 Hz), 3.99 (2 H, t, J = 7.2 Hz), 3.76 (1 H, d, J = 12.0 Hz), 3.66 (1H, d, J = 12.0 Hz), 3. 49 (1 H, t, J = 10.5 Hz), 3. 45 (1 H, t, J = 10.5 Hz), 3. 19 (1 H, br), 3. 13 (1 H, br), 2. 85 (1H, t, J = 10.5 Hz), 2.81 (1 H, t, J = 10.5 Hz), 1. 85 (2 H, sextet, J = 7.2 Hz), 1.06 (3 H, t, J = 7.2 Hz); ^13C NMR _{(151 MHz, CDCl 3) δ} 169.7, 163.2, 152.1, 149.8, 130.0, 126.4, 125.5, 115.0, 95.3, 70.1, 45.8, 43.7, 43.5, 22.5, 10.6, one carbon atom was not found due to overlapping; IR ( film) 2936, 2903, 1790, 1717, 1593, 1329, 1329, 1229, 1219, 1088, 1059, 1016, 972, 925 cm- ¹ ; HRMS (ESI) Calcd for C ₁₈ H ₂₂ O ₇ N ₂ NaS ⁺ ([M + Na] ⁺ ) 433.1040, Found 433.1042.

[Compound 13] White solid (94 mg, yield 44%). ¹ H NMR (600 MHz, CDCl ₃ ) δ 7.65 (2 H, d, J = 9.0 Hz), 7.27 (1 H, d, J = 6.0 Hz), 6.99 (2 H, d, J = 9.0 Hz), 6.96 (1 H , m), 6.28 (1 H, d, J = 6.0 Hz), 4.03 (2 H, t, J = 7.2 Hz), 3. 76 (1 H, d, J = 10.2 Hz), 3. 66 (1 H, d, J = 10.8 Hz) ), 3.49 (1H, t, J = 9.0 Hz), 3.44 (1 H, t, J = 9.0 Hz), 3.19 (1 H, br), 3.12 (1 H, br), 2. 85 (1 H, t, J = 9.0 Hz) ), 2.81 (1 H, t, J = 9.0 Hz), 1.80 (2 H, quintet, J = 7.2 Hz), 1.51 (2 H, sextet, J = 7.2 Hz), 0.99 (3 H, t, J = 7.2 Hz); ¹³ C NMR (151 MHz, CDCl ₃ ) δ 169.6, 163.2, 152.2, 140.0, 126.4, 125.5, 115.0, 95.4, 68.4, 45.8, 43.7, 43.5, 31.2, 19.3, 13.9, one carbon atom was not found due HRMS (ESI) Calcd for C ₁₉ H ₂₄ O ₇ N ₂ NaS ⁺ ([tollapping; IR (film)) 2961, 2934, 2872, 1792, 1719, 1595, 1435, 1342, 1162, 1092 cm ^-1 ; M + Na] ⁺ ) 447.1196, Found 447.1193.

[Compound 14] White solid (150 mg, yield 68%). ¹ H NMR (600 MHz, CDCl ₃ ) δ 7.66 (2 H, d, J = 7.2 Hz), 7.27 (1 H, dd, J = 5.4, 1.2 Hz), 6.99 (2 H, d, J = 9.0 Hz), 6.96 (1H, brs), 6.29 (1 H, d, J = 5.4 Hz), 4.02 (2 H, t, J = 7.2 Hz), 3. 77 (1 H, brd, J = 12.6 Hz), 3. 66 (1 H, brd, J = 12.6 Hz), 3.49 (1H, t, J = 12.6 Hz), 3.45 (1 H, t, J = 12.0 Hz), 3.19 (1 H, t, J = 5.4 Hz), 3.13 (1 H, t, J = 5.4 Hz) ), 2.85 (1 H, t, J = 8.4 Hz), 2. 80 (1 H, t, J = 8.4 Hz), 1.82 (2 H, quintet, J = 7.2 Hz), 1. 45 (2 H, quintet, J = 7.2 Hz), 1.40 (2 H, sextet, J = 7.2 Hz), 0.94 (3 H, t, J = 7.2 Hz); ¹³ C NMR (151 MHz, CDCl ₃ ) δ 169.7, 163.2, 152.2, 149.7, 130.0, 126.4, 125.5, 115.0 , 95.4, 68.7, 45.8, 43.7, 48.9, 28.9, 28.2, 1 14. one carbon atom was not found due to overlapping; IR (film) 2934, 2870, 1790, 1753, 1595, 1433, 1350, 1281, 1217 , 1184, 1140, 1092, 1016 , 966 cm -1; HRMS (ESI) Calcd for C 20 H 26 O 7 N 2 NaS + ([M + Na] +) 461.1353, Found 461.1354.

[Compound 15] White solid (24 mg, yield 66%). ¹ H NMR (600 MHz, CDCl ₃ ) δ 7.62 (2 H, d, J = 8.4 Hz), 7. 35 (2 H, d, J = 8.4 Hz), 7. 27 (1 H, d, J = 5.4 Hz), 6. 95 (1 H , s), 6.28 (1 H, d, J = 5.4 Hz), 3. 76 (1 H, d, J = 10.2 Hz), 3. 66 (1 H, d, J = 10.2 Hz), 3. 48 (1 H, t, J = 10.2 Hz) ), 3.45 (1H, t, J = 10.2 Hz), 3.20 (1 H, brs), 3.14 (1 H, brs), 2. 85 (1 H, t, J = 8.4 Hz), 2.81 (1 H, t, J = 8.4 Hz) ), 2.45 (3H, s); ¹³ C NMR (151 MHz, CDCl ₃ ) δ 169.6, 152.1, 149.8, 144.4, 132.2, 130.1, 127.8, 125.4, 95.3, 45.8, 43.7, 43.5, 21.7, one carbon atom was not found due to overlapping; IR (film) 2924, 2855, 1792, 1721, 1435, 1348, 1242, 1162, 1125, 1088, 1018, 928 cm- ¹ ; HRMS (ESI) Calcd for C ₁₆ H ₁₈ O ₆ N ₂ NaS ^<+> ([M + Na] ^< +>) 389.0778, Found 389.0785.

[Compound 16] White solid (110 mg, yield 58%). ¹ H NMR (600 MHz, CDCl ₃ ) δ 7.65 (2 H, d, J = 8.4 Hz), 7. 37 (2 H, d, J = 8.4 Hz), 7. 27 (2 H, d, J = 6.0 Hz), 6. 96 (1 H , s), 6.29 (1H, d, J = 6.0 Hz), 3.78 (1 H, d, J = 12.0 Hz), 3.67 (1 H, d, J = 12.0 Hz), 3.48 (1 H, t, J = 9.3 Hz) ), 3.44 (1H, t, J = 9.3 Hz), 3.22 (1H, t, J = 6.6 Hz), 3.16 (1 H, t, J = 6.6 Hz), 2.86 (1 H, t, J = 8.4 Hz), 2.82 (1 H, t, J = 8.4 Hz), 2. 75 (2 H, q, J = 7.8 Hz), 1. 29 (3 H, t, J = 7.8 Hz); ¹³ C NMR (151 MHz, CDCl ₃ ) δ 169.6, 152.2 , 150.5, 149.7, 132.5, 128.9, 125.5, 95.4, 45.8, 43.5, 29.0, 15.2, one carbon atom was not found due to overlapping; IR (film) 2974, 2866, 1792, 1721, 1435, 1348 , 1242, 1165, 1090, 1018, 928 cm ^-1 ; HRMS (ESI) Calcd for C ₁₇ H ₂₀ O ₆ N ₂ NaS ⁺ ([M + Na] ⁺ ) 403.0934, Found 403.0333.

[Compound 17] White solid (138 mg, yield 65%). ¹ H NMR (600 MHz, CDCl ₃ ) δ 7.64 (2 H, d, J = 7.5 Hz), 7. 35 (2 H, d, J = 7.5 Hz), 7. 27 (1 H, d, J = 6.0 Hz), 6. 96 (1 H , s), 6.29 (1H, d, J = 6.0 Hz), 3.77 (1 H, d, J = 12.6 Hz), 3.67 (1 H, d, J = 12.6 Hz), 3.49 (1 H, t, J = 10.2 Hz) ), 3.45 (1H, t, J = 10.2 Hz), 3.21 (1 H, t, J = 7.2 Hz), 3.16 (1 H, t, J = 7.2 Hz), 2.87 (1 H, t, J = 8.4 Hz), 2.82 (1 H, t, J = 8.4 Hz), 2. 68 (2 H, t, J = 7.8 Hz), 1. 65 (2 H, quintet, J = 7.8 Hz), 1.39-1 .30 (4 H, m), 0.91 (3 H, t , J = 7.8 Hz); ¹³ C NMR (151 MHz, CDCl ₃ ) δ 169.6, 152.2, 149.7, 149.3, 132.5, 127.9, 125.5, 95.4, 45.8, 43.8, 43.6, 36.0, 31.6, 30.8, 22.6, IR (film) 2926, 2860, 1794, 1721, 1435, 1350, 1242, 1165, 1125, 1090, 1016, 926 cm- ¹ ; HRMS (ESI) Calcd for C. 14.1. One carbon atom was not found due to overlapping; ₂₀ H ₂₆ O ₆ N ₂ NaS ⁺ ([M + Na] ⁺ ) 445.1404, Found 445.1408.

Compound 18 white solid (109 mg, 52% yield). ¹ H NMR (600 MHz, CDCl ₃ ) δ 7.89 (2 H, d, J = 8.7 Hz), 7.84 (2 H, d, J = 8.7 Hz), 7.27 (1 H, dd, J = 5.4, 1.2 Hz), 6.96 (1 H, s), 6.29 (1 H, d, J = 5.4 Hz), 3. 78 (1 H, d, J = 12.3 Hz), 3. 68 (1 H, d, J = 12.3 Hz), 3.53 (1 H, t, J = 7.8 Hz), 3.49 (1 H, t, J = 7.8 Hz), 3. 24 (1 H, t, J = 4.0 Hz), 3. 18 (1 H, t, J = 4.0 Hz), 2. 96 (1 H, t, J = 8.2 Hz) ), 2.92 (1 H, t, J = 8.2 Hz); ¹³ C NMR (151 MHz, CDCl ₃ ) δ 169.6, 152.1, 149.6, 139.3, 135.2 (q, J _CF = 33.2 Hz), 128.3, 126.7 (q, J _CF = 4.4 Hz), 125.6, 123.2 (q, J _CF = 273.3 Hz), 95.4, 45.7, 43.7, 43.5, one carbon atom was not found due to overlapping; IR (film) 2934, 2920, 2874, 1792, 1722, 1595, 1435, 1323, 1242, 1126, 1026, 1063, 957 cm- ¹ ; HRMS (ESI) Calcd for C ₁₆ H ₁₅ O ₆ N ₂ F ₃ NaS ⁺ ([M + Na] ⁺ ) 443.0495 , Found 443.0494.

[Compound 19] White solid (38 mg, yield 88%). ¹ H NMR (600 MHz, CDCl ₃ ) δ 7.89-7.86 (1H, m), 7.78-7.75 (1 H, m), 7.67 (1 H, d, J = 7.2 Hz), 7.45 (1 H, t, J = 7.8) Hz), 7.28 (1 H, d, J = 6.0 Hz), 6.96 (1 H, brs), 6.30-6. 29 (1 H, m), 3. 76 (1 H, brs), 3. 66 (1 H, brs), 3.53 (1 H, t) , J = 11.0 Hz), 3.48 (1 H, t, J = 11.0 Hz), 3.21 (1 H, brs), 3.15 (1 H, brs), 2. 95 (1 H, t, J = 8.4 Hz), 2. 90 (1 H, t , J = 8.4 Hz); ¹³ C NMR (151 MHz, CDCl ₃ ) δ 169.6, 152.2, 149.7, 136.5, 136.5, 130.6, 126.3, 125.5, 123.6, 95.4, 45.8, 43.5, one carbon atom was not found due to overlapping; IR ( film) 2922, 2862, 1792, 1721, 1435, 1352, 1242, 1171, 1126, 1086, 1018, 931 cm -1; HRMS (ESI) Calcd for C 15 H 15 O 6 N ₂ < ⁷⁹ > BrNaS <^+> ([M + Na] ^< +>) 452.9726, Found 452.9723.

Compound 20 white solid (160 mg, 42% yield). ¹ H NMR (600 MHz, CDCl ₃ ) δ 8.42 (2 H, d, J = 8.7 Hz), 7.94 (2 H, d, J = 8.7 Hz), 7.27 (1 H, d, J = 5.4 Hz), 6.95 (1 H , s), 6.29 (1 H, d, J = 5.4 Hz), 3.81 (1 H, d, J = 12.6 Hz), 3.70 (1 H, d, J = 12.6 Hz), 3.52 (1 H, t, J = 11.4 Hz ), 3.48 (1H, t, J = 11.4 Hz), 3.28 (1 H, br), 3.22 (1 H, br), 2. 96 (1 H, t, J = 7.8 Hz), 2. 92 (1 H, t, J = 7.8 Hz) ¹³ C NMR (151 MHz, CDCl ₃ ) δ 169.5, 152.1, 150.7, 149.6, 149.0, 129.0, 124.8, 95.4, 45.7, 43.8, 43.5, one carbon atom was not found due to overlapping; HRMS (ESI) Calcd for C ₁₅ H ₁₅ O ₈ N ₃ NaS ⁺ ([M + Na]) 2981, 2855, 1794, 1719, 1531, 1352, 1244, 1171, 1088, 1018, 932 cm ^-1 ; ⁺ ) 420.0472, Found 420.0466.

[Compound 21] White solid (7 mg, yield 46%). ¹ H NMR (600 MHz, CDCl ₃ ) δ 7.65 (2 H, d, J = 9.0 Hz), 6.99 (2 H, d, J = 9.0 Hz), 6.85-6.83 (1 H, m), 6.81-6.80 (1 H, m), 4.03 (2H, t, J = 6.6 Hz), 3. 76 (1 H, d, J = 12.6 Hz), 3.67 (1 H, d, J = 12.6 Hz), 3.48 (1 H, t, J = 9.6 Hz) , 3.44 (1 H, t, J = 9.6 Hz), 3.19 (1 H, t, J = 6.6 Hz), 3. 13 (1 H, t, J = 6.6 Hz), 2. 84 (1 H, t, J = 9.6 Hz), 2.79 (1H, t, J = 9.6 Hz), 2.34 (2H, q, J = 7.4 Hz), 1.80 (2H, quintet, J = 6.6 Hz), 1.51 (2H, sextet, J = 6.6 Hz), 1.18 (3H , t, J = 7.4 Hz), 0.99 (3 H, t, J = 6.6 Hz); ¹³ C NMR (151 MHz, CDCl ₃ ) δ 170.7, 163.2, 152.4, 140.7, 140.6, 130.0, 126.4, 115.0, 94.1, 68.4, 45.8, 43.7, 43.4, 31.2, 19.3, 18.9, 11.5, one carbon atom was not found due to overlapping; IR (film) 2961, 2936, 2874, 1778, 1721, 1595, 1464, 1435, 1350, 1242, 1161, 1125, 1092, 1020, 947 cm ⁻¹ ; HRMS (ESI) Calcd for C ₂₁ H ₂₈ O ₇ N ₂ NaS ⁺ ([M + Na] ⁺ ) 475.1509, Found 475.1505.

Compound 22 white solid (58 mg, 66% yield). ¹ H NMR (600 MHz, CDCl ₃ ) δ 7.65 (2 H, d, J = 9.0 Hz), 7.00 (2 H, d, J = 9.0 Hz), 6.74 (1 H, brs), 5.93 (1 H, brs), 4.03 (2H, t, J = 7.2 Hz), 3.81 (1H, d, J = 10.4 Hz), 3.70 (1H, d, J = 10.4 Hz), 3.50-3.39 (2H, m), 3.25 (1H, brs) , 3.18 (1H, brs), 2.80 (1H, t, J = 8.7 Hz), 2.76 (1H, t, J = 8.7 Hz), 2.05 (3H, s), 1.80 (2H, quintet, J = 7.2 Hz) , 1.51 (2 H, sextet, d, J = 7.2 Hz), 0.99 (3 H, t, J = 7.8 Hz); ¹³ C NMR (151 MHz, CDCl ₃ ) δ 169.9, 163.2, 162.7, 152.5, 129.9, 126.3, 119.7, 115.0, 96.1, 68.3, 45.8, 43.5, 31.1, 19.3, 13.4, one carbon atom was not found due to overlapping; IR (film) 2961, 2932, 2872, 1792, 1917, 1593, 1435, 1348, 1240, 1159, 1088, 1022, 978 cm -1; HRMS (ESI) Calcd for C 20 H 26 O 7 N 2 NaS + ([M + Na] +) 461.1353, Found 461.1349.

[Compound 23] White solid (66 mg, yield 73%). ¹ H NMR (600 MHz, CDCl ₃ ) δ 7.65 (2 H, d, J = 9.0 Hz), 6.99 (2 H, d, J = 9.0 Hz), 6.67 (1 H, s), 4.03 (2 H, t, J = 6.6 Hz), 3.82 (1 H, d, J = 12.3 Hz), 3.70 (1 H, d, J = 12.3 Hz), 3.44 (1 H, t, J = 10.4 Hz), 3.40 (1 H, t, J = 10.4 Hz) ), 3.25 (1H, d, J = 9.3 Hz), 3.18 (1H, d, J = 9.3 Hz), 2.78 (1 H, t, J = 9.0 Hz), 2.73 (1 H, t, J = 9.0 Hz), 1.93 (3H, s), 1.85 (3H, s), 1.80 (2H, quintet, J = 6.6 Hz), 1.51 (2H, sextet, J = 6.6 Hz), 0.99 (3 H, t, J = 6.6 Hz); ¹³ C NMR (151 MHz, CDCl ₃ ) δ 171.7, 163.2, 153.3, 159.9, 129.9, 126.4, 126.4, 115.0, 68.4, 45.8, 43.7, 43.5, 31.2, 19.3, 13.9, 11.5, 8.7, one carbon atom IR (film) 2959, 2928, 2872, 1775, 1722, 1595, 1435, 1310, 1240, 1161, 1123, 1084, 989 cm- ¹ ; HRMS (ESI) Calcd for C _{21 ^{H 28 O 7 N 2 NaS +}} ([M + Na] +) 475.1509, Found 475.1506.

Compound 24 white solid (155 mg, yield 67%). ¹ H NMR (600 MHz, CDCl ₃ ) δ 7.65 (2 H, d, J = 9.0 Hz), 6.99 (2 H, d, J = 9.0 Hz), 6.86-6.83 (2 H, m), 5. 85 (1 H, ddt, J = 16.8, 10.8, 6.9 Hz), 5.20 (1 H, dd, J = 16.8, 1.2 Hz), 5.19 (1 H, dd, J = 10.8, 1.2 Hz), 4.03 (2 H, t, J = 7.2 Hz), 3.75 (1 H, d, J = 12.6 Hz), 3.66 (1 H, d, J = 12.6 Hz), 3.48 (1 H, t, J = 9.6 Hz), 3.44 (1 H, t, J = 9.6 Hz), 3.17 (3 1H, br), 3.11 (1H, br), 3.06 (2H, d, J = 6.9 Hz), 2.85 (1 H, t, J = 7.8 Hz), 2.80 (1 H, t, J = 7.8 Hz), 1.80 ( 2 H, quintet, J = 7.2 Hz), 1.51 (2 H, sextet, J = 7.2 Hz), 0.99 (3 H, t, J = 7.2 Hz); ¹³ C NMR (151 MHz, CDCl ₃ ) δ 170.3, 163.2, 152.3 , 142.1, 137.5, 132.1, 129.9, 128.9, 115.0, 114.0, 94.0, 48.4, 43.7, 43.4, 31.2, 29.6, 19.3, 13.9, one carbon atom was not found due to overlapping; IR (film) 2961, 2932 HRMS (ESI) Calcd for C ₂₂ H ₂₈ O ₇ N ₂ NaS ⁺ ([M + Na], 2870, 1778, 1722, 1595, 1497, 1348, 1242, 1159, 1015, 964 cm ^-1 ; ⁺ ) 487.1509, Found 487.1493.

[Compound 25] White solid (113 mg, yield 83%). ¹ H NMR (600 MHz, CDCl ₃ ) mixture of rotamers δ 7.71-7.66 (2 + 2 H, m), 6.97 (2 + 2 H, d, J = 8.4 Hz), 6.89 (1 H, q, J = 1.2 Hz) , 6.88 (1H, q, J = 1.2 Hz), 6.87 (1 H, s), 6.86 (1 H, s), 4.02 (2 + 2 H, t, J = 6.8 Hz), 3.74-3.67 (1 H, m), 3.65-3.39 (5 + 6H, m), 3.18 (1H, ddd, J = 13.8, 7.8, 3.6 Hz), 3.12-3.01 (1 + 2H, m), 2.01-1.93 (4 + 4H, m), 1.93 -1.86 (1 + 1H, m), 1.79 (2 + 2H, quintet, J = 6.6 Hz), 1.50 (2 + 2H, sextet, J = 6.8 Hz), 0.98 (3 + 3 H, t, J = 6.8 Hz ; ¹³ C NMR (151 MHz, CDCl ₃ ) mixture of rotamers δ 171.3 ₂ , 171.2 ₉ , 162.7, 153.6, 153.2, 142.4, 142.3, 134.5, 130.4 ₀ , 130.3 ₇ , 129.0 ₇ , 129.0 ₅ , 114.9, IR (film) 2957, 2872, 1780, 1721, 1713, 1595, 1423, 1331, 93.8, 68.3, 49.8, 48.9, 47.8, 46.5, 46.5, 46.2, 28.3, 23.9, 13.9, 10.7; 1256, 1153, 1092, 1013, 959 cm -1; HRMS (ESI) Calcd for C 21 H 28 O 7 N 2 NaS + ([M + Na] +) 475.1509, Found 475.1510.

[Compound 26] colorless oil (39 mg, 29% yield). ¹ H NMR (600 MHz, CDCl ₃ ) mixture of rotamers δ 7.69 (2 H, dd, J = 9.0, 2.4 Hz), 7.68 (2 H, dd, J = 9.0, 2.4 Hz), 7.33 (1 H, d, J = 6.0 Hz), 7.31 (1 H, d, J = 6.0 Hz), 7.00 (1 H, s), 6.99 (1 H, s), 6. 97 (2 + 2 H, d, J = 9.0 Hz), 6. 29 (1 +1 H, s) d, J = 6.0 Hz), 4.02 (2 + 2 H, t, J = 6.6 Hz), 3.75-3.69 (1 H, m), 3.64 (1 H, dt, J = 13.8, 6.6 Hz), 3.60-3.41 (5 + 5H, m), 3.18 (1H, ddd, J = 13.8, 7.8, 3.0 Hz), 3.13-3.00 (1 + 2H, m), 2.04-1.85 (2 + 2H, m), 1.79 (2 + 2H, m) quintet, J = 7.2 Hz), 1.50 (2 + 2 H, sextet, J = 7.2 Hz), 0.98 (3 + 3 H, t, J = 7.2 Hz); ¹³ C NMR (151 MHz, CDCl ₃ ) mixture of rotamers δ 169.9, 169.8, 162.7, 153.4, 153.0, 150.1, 150.0, 130.4 _0, 130.3 _7, 129.0 _9, 129.0 _6, 125.4, 125.3, 115.0, 95.4, 68.3, 49.7 _1, 49.6 ₇ 48.9, 47.9, 47.7, 46.7, IR (film) 2959, 2872, 1790, 1715, 1593, 1472, 1423, 1331, 1254, 1152, 1088, 1015 cm- ¹ ; HRMS (ESI) Calcd for C. 46.1, 31.2, 28.3, 27.9, 19.3; ₂₀ H ₂₆ O ₇ N ₂ NaS ⁺ ([M + Na] ⁺ ) 461.1353, Found 461.1352.

<Synthesis of Compound 27>
Compound 27 was synthesized according to the following synthesis scheme.

Step: 1
A solution of ethylenediamine (10) (4.0 mL, 60 mmol, 5 equiv.) In dichloromethane (120 mL) is cooled to 0 ° C., and 4-butoxybenzene-1-sulfonyl chloride (1a) (3.0 g, 12 mmol, 1 equiv) ) And triethylamine (2.0 mL, 14.4 mmol, 1.2 equiv.) Were added, and the reaction solution was stirred for 1 hour while slowly returning to room temperature. The solvent was evaporated, diluted with diethyl ether (10 mL) and washed (x 3) with dilute hydrochloric acid (1 N, 5 mL). The aqueous layer was adjusted to pH 10 with aqueous potassium carbonate solution, extracted with ethyl acetate (5 mL) (× 3), dried over anhydrous Na ₂ SO ₄ and concentrated to give an amine (11) as a white solid (1.5) g, 47% yield).

Step: 2
Amine (11) (27 mg, 0.10 mmol, 1 equiv), paraformaldehyde (15 mg, 0.50 mmol, 5 equiv), potassium carbonate (48 mg, 0.35 mmol, 3.5 equiv), and magnesium sulfate (42 mg, 0.35 mmol) , 3.5 equiv) in chloroform (0.2 mL) and stirred at room temperature overnight under an argon atmosphere. The reaction solution was filtered through celite, the obtained filtrate was concentrated, and the residue was purified by silica gel column (eluent: mixed solvent of hexane / ethyl acetate) to obtain amine (3c) as white solid (24 mg, Yield 85%).

Step: 3
A solution of triphosgene (18 mg, 0.06 mmol, 1 equiv.) In dichloromethane (0.3 mL) is cooled to 0 ° C., amine (3c) (17 mg, 0.06 mmol, 1 equiv.), And triethylamine (25 μL, 0.18 mmol) , 3 equiv.) Was added and stirred for 2 hours under argon atmosphere. While maintaining the reaction solution at 0 ° C, dichloromethane (0.6 mL), 5-hydroxy-3-methyl-2-furanone (4a) (21 mg, 0.18 mmol, 3 equiv.), Triethylamine (25 μL, 0.18 mmol, 3 equiv., And N, N-dimethyl-4-aminopyridine (0.7 mg, 0.006 mmol, 10 mol%) were added, and the reaction solution was stirred overnight while slowly returning to room temperature. The reaction was quenched with saturated sodium bicarbonate, extracted with dichloromethane (3 mL) (x 3) and dried over anhydrous Na ₂ SO ₄ . The solvent was evaporated and then the residue was purified by silica gel column (eluent: mixed solvent of hexane / ethyl acetate) to obtain white solid target compound (12) (compound 27) (21 mg, yield 82%) ).
¹ H NMR (600 MHz, CDCl ₃ ) rotamer A δ 7.73 (2 H, d, J = 9.0 Hz), 7.02 (2 H, d, J = 9.0 Hz), 6.88 (1 H, s), 6.81 (1 H, s) , 4.68 (1 H, d, J = 9.0 Hz), 4.62 (1 H, d, J = 9.0 Hz), 4.09-4.01 (2 H, m), 3.57 (1 H, dt, J = 12.0, 6.0 Hz), 3.53- 3.48 (1 H, m), 3.32 (1 H, dt, J = 9.6, 6.6 Hz), 3.26-3.18 (1 H, m), 2.02 (3 H, s), 1.84-1.77 (2 H, m), 1.51 (2 H, sextet, J = 7.8 Hz), 0.99 (3 H, t, J = 7.8 Hz); rotamer B δ 7.76 (2 H, d, J = 9.0 Hz), 7.00 (2 H, d, J = 9.0 Hz), 6.81 (1 H) , s), 6.79 (1H, s), 4.72 (2H, s), 4.09-4.01 (2H, m), 3.60 (1H, dt, J = 12.0, 6.0 Hz), 3.53-3.48 (1H, m), 3.26-3.18 (2H, m), 1.96 (3H, s), 1.84-1.77 (2H, m), 1.51 (2H, sextet, J = 7.8 Hz), 0.99 (3 H, t, J = 7.8 Hz); ¹³ _{C NMR (151 MHz, CDCl 3} ) mixture of rotamers δ 171.1, 171.0, 163.6 3, 163.5 8, 150.9, 150.6, 141.8 9, 141.8 6, 134.9, 134.7, 130.0, 129.8, 127.2 3, 127.1 8, 115.4, 115.2 , 93.5, 68.5 ₁ , 68.4 ₈ , 62.5, 61.9, 47.2, 46.4, 44.0, 31.1, 19.3, 10.8, 10.7; IR (film) 2959, 2874, 1778, 1726, 1526, 1423, 1422, 1348, 1260 , ^{1157, 1092, 959 cm -1;} HRMS (ESI) Calcd for C 19 H 24 O 7 N 2 NaS + ([M + Na] +) 447.1196, Found 447.1191.

<Synthesis of Compound 28>
According to the synthesis method of Compound 27, synthesis was carried out using appropriate material compounds.

Compound 28 white solid (16 mg, 45% yield). ¹ H NMR (600 MHz, CDCl ₃ ) rotamer A δ 7.73 (2 H, d, J = 9.0 Hz), 7.31 (1 H, d, J = 6.0 Hz), 7.02 (2 H, d, J = 9.0 Hz), 6.94 (1H, s), 6.35 (1H, d, J = 6.0 Hz), 4.68 (1 H, d, J = 9.0 Hz), 4.63 (1 H, d, J = 9.0 Hz), 4.09-4.01 (2H, m) , 3.57 (1H, dt, J = 12.0, 6.0 Hz), 3.51 (1H, dt, J = 12.0, 6.0 Hz), 3.33 (1H, dt, J = 9.6, 6.0 Hz), 3.29-3.19 (1H, m) ), 1.80 (2H, quintet, J = 7.2 Hz), 1.51 (2H, sextet, J = 7.2 Hz), 0.99 (3H, t, J = 7.2 Hz); rotamer B δ 7.77 (2H, d, J = 9.0) Hz), 7.24 (1 H, d, J = 6.0 Hz), 7.01 (2 H, d, J = 9.0 Hz), 6.92 (1 H, s), 6.28 (1 H, d, J = 6.0 Hz), 4.72 (2 H, s), 4.09-4.01 (2H, m), 3.61 (1H, dt, J = 12.0, 6.0 Hz), 3.51 (1H, dt, J = 12.0, 6.0 Hz), 3.29-3.19 (2H, m), 1.80 (2H, quintet, J = 7.2 Hz), 1.51 (2H, sextet, J = 7.2 Hz), 0.99 (3H, t, J = 7.2 Hz); ¹³ C NMR (151 MHz, CDCl ₃ ) mixture of rotamers δ 169.6 , 169.5, 163.6 ₄ , 163.5 ₉ , 150.6, 149.6, 127.2, 127.1, 125.6, 125.5, 115.5, 115.2, 95.0, 68.5 ₁ , 68.4 ₇ , 62.5, 61.9, 47.2, 46.4, 44.3, 44.1 , 31.1, HRMS (ESI) Calcd for C ₁₈ H ₂₂ O ₇ N ₂ NaS ⁺ (IR, film) 2959, 2874, 1792, 1728, 1532, 1420, 1260, 1157, 1086, 1009 cm ^-1 ; HRMS (ESI) [M + Na] ^< +>) 433.1040, Found 433.1031.

<Synthesis of Compound 29>
Compound 29 was synthesized according to the following synthesis scheme.

Step: 1
To a solution of ethyl 4-piperidinecarboxylate (13) (0.15 mL, 1.0 mmol, 1 equiv.) In dichloromethane (10 mL), 4-butoxybenzene-1-sulfonyl chloride (1a) (0.25 g, 1.0 mmol, 1 equiv.) And triethylamine (0.21 mL, 1.5 mmol, 1.5 equiv.) Were added and stirred at room temperature overnight, and then quenched with saturated sodium bicarbonate. The reaction mixture was extracted (× 3) with dichloromethane (5 mL) and dried over anhydrous Na ₂ SO ₄ . After evaporation of the solvent, the residue was purified by silica gel column (eluent: mixed solvent of hexane / ethyl acetate) to obtain sulfonamide (14) as white solid (0.32 g, yield 87%).

Step: 2
Lithium hydroxide monohydrate (63 mg, 1.5 mmol, 5 equiv), and sulfonamide (14) (110 mg, 0.3 mmol, 1 equiv) mixed with tetrahydrofuran (1.5 mL) and water (1.5 mL) Stir in solution overnight at room temperature. The reaction mixture is diluted with water, extracted with diethyl ether (5 mL) (x 3), the aqueous layer is adjusted to pH 2 with potassium hydrogen sulfate and then extracted with ethyl acetate (5 mL) (x 3), dried Drying over Na ₂ SO ₄ and concentration gave sulfonamide (15) as a white solid (94 mg, 92% yield).

Step: 3
A solution of sulfonamide (15) (34 mg, 0.10 mmol, 1 equiv.) In dichloromethane (1 mL) is cooled to 0 ° C., oxalyl chloride (9.4 μL, 0.11 mmol, 1.1 equiv.), And N, N-dimethyl Formamide (1 drop) was added and stirred for 5 hours while slowly returning to room temperature under argon atmosphere. The reaction solution is concentrated and then dichloromethane (1 mL), 5-hydroxy-2-furanone (4b) (30 mg, 0.3 mmol, 3 equiv.), Triethylamine (42 μL, 0.3 mmol, 3 equiv.), And N , N-Dimethyl-4-aminopyridine (1 mg, 0.01 mmol, 10 mol%) was added at 0 ° C, and the reaction solution was stirred overnight while slowly returning to room temperature. The reaction was quenched with saturated sodium bicarbonate, extracted with dichloromethane (3 mL) (x 3) and dried over anhydrous Na ₂ SO ₄ . The solvent was evaporated and then the residue was purified by silica gel column (eluent: mixed solvent of hexane / ethyl acetate) to obtain white solid target compound (16) (compound 29) (13 mg, yield 31%) ).
¹ H NMR (600 MHz, CDCl ₃ ) δ 7.67 (2 H, d, J = 9.0 Hz), 7.29 (1 H, d, J = 5.4 Hz), 6.98 (2 H, d, J = 9.0 Hz), 6.97 (1 H , s), 6.31 (1 H, d, J = 5.4 Hz), 4.02 (2 H, t, J = 7.8 Hz), 3.65-3.59 (2 H, m), 2.48 (2 H, t, J = 11.4 Hz), 2. 39 -2.33 (1H, m), 2.00 (2H, t, J = 9.6 Hz), 1.88-1.77 (4H, m), 1.51 (2H, sextet, J = 7.8 Hz), 0.99 (3H, t, J = 7.8) ^{Hz); 13 C NMR (151} MHz, CDCl 3) δ 172.1, 169.5, 162.9, 149.5, 129.8, 127.4, 125.5, 114.8, 94.0, 68.3, 45.2 8, 45.2 5, 40.0, 31.2, 27.3, 19.3, 13.9, IR (film) 2959, 2934, 2872, 1792, 1757, 1595, 1497, 1335, 1260, 1155, 1086, 1009, 928 cm- ¹ ; HRMS (ESI) Calcd for C. one carbon atom was not found due to overlapping; ₂₀ H ₂₅ O ₇ N NaS ⁺ ([M + Na] ⁺ ) 446.1244, Found 446.1240.

<Synthesis of Compound 30>
Compound 30 was synthesized according to the following synthesis scheme.

Step: 1
(S) -N-Boc-2-hydroxymethylmorpholine (1) (21.7 mg, 0.1 mmol, 1 equiv.), 2-tert-butylphenol (2) (18.4 μL, 0.12 mmol, 1.2 equiv), and triphenyl A solution of phosphine (31.5 mg, 0.12 mmol, 1.2 equiv) in tetrahydrofuran (1 mL) is cooled to 0 ° C., di-tert-butylazodicarboxylate (27.6 mg, 0.12 mmol, 1.2 equiv) is added, and the atmosphere is argon. The reaction solution was stirred overnight while slowly returning to room temperature. The reaction solution diluted with water was extracted with ethyl acetate (5 mL) (x 3), and the organic layer was washed with a saturated aqueous sodium chloride solution and then dried over anhydrous Na2SO4. After the solvent was evaporated, the residue was purified by silica gel column (eluent: mixed solvent of hexane / ethyl acetate) to obtain amide (3) as yellow oil (24.4 mg, yield 70%).

Step: 2
The amide (3) (24.4 mg, 0.07 mmol, 1 equiv), and 6N hydrochloric acid / methanol solution (0.35 mL) were stirred at 50 ° C. overnight. The solvent was evaporated and the residue was dissolved in water (5 mL) and washed with diethyl ether. The obtained aqueous layer was adjusted to pH 9 with sodium hydrogen carbonate, extracted with ethyl acetate (5 mL) (× 3), and the organic layer was dried over anhydrous Na 2 SO 4. After evaporation of the solvent, the residue was purified by silica gel column (eluent: mixed solvent of chloroform / methanol) to obtain amine (4) as yellow oil (8.3 mg, yield 47%).

Step: 3
A solution of triphosgene (9.8 mg, 0.033 mmol, 1 equiv) in dichloromethane (1.0 mL) is cooled to 0 ° C., amine (4) (8.3 mg, 0.033 mmol, 1 equiv.), And triethylamine (14 μL, 0.099 mmol, 3 equiv) was added and stirred for 2 hours under argon atmosphere. While maintaining the reaction solution at 0 ° C, dichloromethane (3.6 mL), 5-hydroxy-5H-2-furanone (5) (10 mg, 0.099 mmol, 3 equiv.), Triethylamine (14 μL, 0.099 mmol, 3 equiv) And N, N-dimethyl-4-aminopyridine (0.4 mg, 0.0033 mmol, 10 mol%) were added, and the reaction solution was stirred overnight while slowly returning to room temperature. To the reaction mixture was added saturated aqueous sodium hydrogen carbonate solution, extracted with dichloromethane (3 mL) (× 3), and the organic layer was dried over anhydrous Na 2 SO 4. The solvent was evaporated and then the residue was purified by silica gel column (eluent: mixed solvent of hexane / ethyl acetate) to obtain colorless oily target compound (6) (compound 30) (10.2 mg, yield 82%) ).
¹ H NMR (600 MHz, CDCl ₃ ) mixtures of diastereomers and rotamers δ 7.36-7.27 (2H, m), 7.17 (1 H, t, J = 8.2 Hz), 7.06 (1 H, br), 6. 92 (1 H, t, J) J = 8.2 Hz), 6.86-6.80 (1 H, m), 6.32 (1 H, d, J = 6.0 Hz), 4.33-4.17 (1 H, m), 4.13-3.80 (5 H, m), 3.73-3.57 (1 H , m), 3.20-3.08 (1H, m), 3.08-3.00 (1H, m), 1.41-1.33 (9H, m); ¹³ C NMR (151 MHz, DMSO-d6) mixtures of diastereomers and rotamers δ 170.9, 157.3, 152.8, 152.5, 137.7, 127.7, 124.7, 121.0, 112.9, 115.9, 95.9, 95.7, 74.0, 68.6, 68.1, 66.2, 66.0, 46.8, 46.1, 44.3, 43.9, 34.9, 30.2; HRMS (ESI) Calcd for C ₂₀ H ₂₅ O ₆ N Na ⁺ ([M + Na] ⁺ ) 2951, 2926, 2864, 1794, 1941, 1443, 1233, 1126, 1015, 978 cm ^-1 ; ) 398.1574, Found 398.1573.

Reference Example 1 Synthesis of Comparative Compound Compound 2 described in Patent Document 1 was synthesized as Comparative Compound 1 by the method described in Patent Document 1. The structural formula of comparative compound 1 is shown below.

Reference Example 2. Synthesis of Probe for Strigolactone Receptor Affinity Evaluation The probe for evaluating strigolactone receptor affinity (YLG) described in Patent Document 2 was synthesized by the method described in Patent Document 2. The structural formula of YLG is shown below.

Example 2 Evaluation of parasitic plant germination control activity The parasitic plant germination induction test was done by making the compound synthesize | combined in Example 1 into the test compound. The seeds of a parasitic plant (Striga hermonthica, Orobanche minor, or Phelipanche aegyptiaca) were suspended in sterile ultrapure water, and aliquoted into 96-well plates in 100 μL aliquots (containing about 20 seeds). Thereto, a test compound dissolved in DMSO, or a reference compound (comparative compound 1 or synthetic strigolactone (GR24: comparative compound 2)), the final concentration of the compound is 10 nM to 1 fM (1 × 10 ^{− The mixture} was added to a ^{concentration of 8} to 1 × 10 ^-15 M), and left in the dark for 2 days. The presence or absence of germination was observed by microscopic observation, and the germination rate (= number of seeds germinated / total number of seeds) was measured. The higher the germination rate of the parasitic plant germination induction test, and the higher the germination rate at a lower concentration, indicate that the strikea germination induction activity is higher.

The results are shown in Tables 1-6. The results of comparison using Striga hermonthica seeds are shown in Tables 1 to 4. The results of comparison using the seeds of Orobanche minor are shown in Table 5. The comparison results using Phelipanche aegyptiaca seeds are shown in Table 6. In Tables 1 to 6, concentrations (10 nM, 1 nM, 0.1 nM) indicate compound concentrations. In Tables 1 to 6, the evaluation criteria for the compounds are as follows:
++: Germination rate of 20% or more
+: Germination rate 5% or more and less than 20%
-: Less than 5% germination rate

As shown in Tables 1 to 4, all of the compounds 1 to 30 exhibited higher parasitic plant sprout regulating activity than the comparative compound 1. In addition, compounds 1 to 30 generally exhibited parasitic plant germination regulatory activity equal to or greater than or equal to that of strigolactones.

Example 3 Evaluation of Affinity for Receptor In Patent Document 1, the affinity of the test compound for the strigolactone receptor is determined by the presence of the strigolactone and the probe for evaluating the strigolactone receptor affinity (such as YLG) as the test compound. It is reported that it can be evaluated by measuring the fluorescence emitted from the decomposition product of YLG by reacting it below. Therefore, using the compound synthesized in Example 1 as a test compound, the affinity to the strigolactone receptor was evaluated by the same method. Specifically, it carried out as follows.

The Arabidopsis thaliana natrigolactone receptor (AtD14) was produced according to a conventional method. Specifically, cDNA of the receptor was obtained by RT-PCR, and was produced by expression and purification in E. coli. In addition, Striga trigolactone receptor (ShHTL1: amino acid sequence is SEQ ID NO: 1; ShHTL2: amino acid sequence is SEQ ID NO: 2; ShHTL3: amino acid sequence is SEQ ID NO: 3; ShHTL4: amino acid sequence is SEQ ID NO: 4; ShHTL5: amino acid sequence is SEQ ID NO: 5, ShHTL6: amino acid sequence SEQ ID NO: 6, ShHTL7: amino acid sequence SEQ ID NO: 7, ShHTL8: amino acid sequence SEQ ID NO: 8, ShHTL9: amino acid sequence SEQ ID NO: 9, ShHTL10: amino acid sequence SEQ ID NO: 10, ShHTL11 : The amino acid sequence produced SEQ ID NO: 11) by the method described in Patent Document 1.

The resulting strigolactone receptor (1 μg each), YLG (final concentration 1 μM), and a test compound (final concentration 0.01 to 10 μM) which is a competitor compound or a control compound (5-deoxystrigol, final concentration 0.01 to 10 μM 100 μL of a reaction solution (100 mM HEPES, 150 mM NaCl, pH 7.0, 0.1% DMSO) containing the above was prepared and reacted in a 96 black well plate (manufactured by Greiner). The fluorescence was detected at an excitation wavelength of 480 nm and a detection wavelength of 520 nm using a fluorescence detector (spectraMax i3, manufactured by Molecular Devices) at 60 hours after the start of the reaction, and the fluorescence intensity was measured. Based on the measurement results of fluorescence intensity, to create a Linewaver-Burk plot to calculate the K _m values, IC ₅₀ values were calculated for each test compound and control compound are competing compounds.

The results are shown in Table 7. In Table 7, HTLs 1 to 11 are Striga trigolactone receptors (SEQ ID NOs: 1 to 11), and AtD14 is an Arabidopsis thaliana trigolactone receptor.

From Table 7, it was suggested that the test compound had an affinity for the Striga trigolactone receptor, and for the HHTL7 considered to be an important receptor among others. In addition, it was found that the test compound has no affinity for the Arabidopsis thaliana trigolactone receptor, and specifically has an affinity for the strigatrigolactone receptor. This suggests that the test compound has less influence on plants (eg, crops) other than parasitic plants.

Claims (12)

1. General formula (1):
   

   

   [Wherein, R ¹ represents a group derived from a hetero ring containing a nitrogen atom. R ² represents a divalent group which is a linker. R ³ represents an aryl group which may be substituted, a heteroaryl group which may be substituted, a cycloalkyl group which may be substituted, or an alkyl group having 1 to 6 carbon atoms. R ⁴ , R ⁵ and R ⁶ are the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group which may be substituted, an alkenyl group which may be substituted, or an alkynyl group which may be substituted. However, when the hetero ring is a polycycle, two bonds of R ¹ are present in ^one of a plurality of rings constituting the polycycle. ]
   A compound represented by
2. The R ¹ is a general formula (Y):
   

   

   [Wherein, R ¹¹ represents-(CHR ^11a- ) _n (n represents an integer of 1 to 3. R ^11a is the same or different and represents a hydrogen atom or an alkyl group, and when n is 2 or 3, two of them R ^11a may be bonded to each other to form a ring with the adjacent carbon atom. R ¹² and R ¹³ are the same or different and each represents a hydrogen atom or an alkyl group, and R ¹² and R ¹³ may be bonded to each other to form a ring with adjacent carbon atoms. R ¹⁴ represents a carbon or nitrogen atom. ]
   Or a divalent group represented by the general formula (Y ′):
   

   

   [Wherein, R ¹⁵ represents a single bond or-(CHR ^15a- ) _m (m represents 1 or 2. R ^15a is the same or different and represents a hydrogen atom or an alkyl group, and when m is 2, adjacent 2 One R ^15a may be bonded to each other to form a ring with the adjacent carbon atom. R ¹⁶ and R ¹⁷ are the same or different and each represents a hydrogen atom or an alkyl group, and R ¹⁶ and R ¹⁷ may be bonded to each other to form a ring with adjacent carbon atoms. ]
   The compound of Claim 1 which is a bivalent group represented by these.
3. Wherein R ² is Formula (Z1): - T-U- ( wherein (Z1), T is, -S (O) _1-2 -, or -C (= O) -, or - (CH _{2) 1-3} - and, U is a single bond, - (CH _{2) 1-3} -, - O-, or -NR ^'- (where, ^R' represents a hydrogen atom or an alkyl group.) a. ) divalent group represented by, or the general formula (Z2): - V-O -W- ( wherein (Z2) in, V is a single bond or - (CH _{2) 1-3} - and is, W is , Single bond,-(CH ₂ ) _1-3- , -C (= O)-, -S (O) _1-2- , or -C (= O) -NR ^' -(where R ^' is hydrogen The compound according to claim 1 or 2, which is a divalent group represented by)) which represents an atom or an alkyl group.
4. Wherein R ² is formula (Z1a): - S (O ) 1-2 -U- [ wherein, U is a single _{bond, - (CH 2) 1-3 -} , - O-, or -NR ^'- (However, R ^' shows a hydrogen atom or an alkyl group.). [Wherein W represents a single bond,-(CH ₂ ) _1-3- , -C (= O)-, -S], or a divalent group represented by the general formula (Z2a): -O-W- (O) _1-2 -, or ^{-C (= O) -NR '-} (. However, ^R' is represents a hydrogen atom or an alkyl group) is a divalent group represented by], claim 1 The compound according to any one of 3.
5. Wherein R ² is -S (O) ₂ - A compound according to claim 3 or 4.
6. The compound according to any one of claims 1 to 5, wherein R ³ is a phenyl group which may be substituted.
7. The compound represented by the general formula (1) is a compound represented by the general formula (1C):
   

   

   [Wherein, R ¹¹ represents-(CHR ^11a- ) _n (n represents an integer of 1 to 3. R ^11a is the same or different and represents a hydrogen atom or an alkyl group, and when n is 2 or 3, two of them R ^11a may be bonded to each other to form a ring with the adjacent carbon atom. R ¹² and R ¹³ are the same or different and each represents a hydrogen atom or an alkyl group, and R ¹² and R ¹³ may be bonded to each other to form a ring with adjacent carbon atoms. R ¹⁴ represents a carbon or nitrogen atom. R ³¹ , R ³² , R ³³ , R ³⁴ , and R ³⁵ are the same or different and each is a hydrogen atom, a halogen atom, an alkyl group which may be substituted, an alkoxy group which may be substituted, or even substituted Good alkylthio group, alkenyl group which may be substituted, alkynyl group which may be substituted, amino group which may be substituted, nitro group, hydroxyl group, cyano group, -C (= O) R ³⁰¹ , -C (= O) OR ³⁰² , -C (= O) NR ³⁰³ R ³⁰⁴ , -S (= O) _1-2 R ³⁰⁵ , -S (= O) _1-2 NR ³⁰⁶ R ³⁰⁷
   Indicates R ⁴ , R ⁵ and R ⁶ are the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group which may be substituted, an alkenyl group which may be substituted, or an alkynyl group which may be substituted. ]
   The compound according to any one of claims 1 to 6, which is a compound represented by
8. The R ⁴ is an alkyl group which may be substituted, an alkenyl group which may be substituted, or an alkynyl group which may be substituted, and both of R ⁵ and R ⁶ may be hydrogen atoms. 8. The compound according to item 7.
9. General formula (1):
   

   

   [Wherein, R ¹ represents a group derived from a hetero ring containing a nitrogen atom. R ² represents a divalent group which is a linker. R ³ represents an aryl group which may be substituted, a heteroaryl group which may be substituted, a cycloalkyl group which may be substituted, or an alkyl group having 1 to 6 carbon atoms. R ⁴ , R ⁵ and R ⁶ are the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group which may be substituted, an alkenyl group which may be substituted, or an alkynyl group which may be substituted. ]
   Parasitic plant germination regulator containing a compound represented by the formula, or an agriculturally acceptable salt, hydrate or solvate thereof
10. The germination regulator according to claim 9, which is a parasitic plant germination inducer.
11. The germination regulator according to claim 9 or 10, wherein the parasitic plant is a Striga plant or an Orobanchi plant.
12. A parasitic plant germination control method comprising applying the parasitic plant germination regulator according to any one of claims 9 to 11 to soil containing seeds of parasitic plants.